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  • 1
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 2 (1947), S. 349-349 
    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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  • 2
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 2 (1947), S. 349-350 
    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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  • 3
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 2 (1947), S. 10-11 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The refractive index-temperature data for polyvinyl acetate show a second-order phase transition temperature of 24°C.
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  • 4
    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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  • 5
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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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  • 6
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 2 (1947), S. 354-354 
    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
    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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  • 8
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The swelling of vulcanized natural rubber, Buna S, neoprene, Perbunan, and Perbunan Extra was measured in various organic liquids. The essential influence of polarizability and polarity on the swelling equilibrium is illustrated by comparing series of solvents and polymers with gradually changing geometrical and chemical structure. Experiments on the influence of temperature and of strain on the swelling equilibrium are reported. The swelling properties of ebonites and similar derivatives allow some conclusions on the amount of cross linking in these polymers.
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  • 9
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 2 (1947), S. 371-380 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Practical, theoretical, and experimental aspects, including sources of error and methods of control, of the water and water vapor permeability of organic membranes are discussed. Determinations of the permeability have been made at two different temperatures. Data are given on: polyethylene (alkathene, Imperial Chemical Industries), polystyrene (Styroflex, D. Seekabelwerke), chlorinated polyvinyl chloride (Vinifol, I. G. farbenindustrie), cellulose acetates (Triacetat, Schering, and Triafol, I. G. Farbenindustrie), a plasticized polyvinyl chloride (Welvic, Imperial Chemical Industries), and a copolymer of vinylidene chloride and vinyl chloride (Saran, Dow).
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  • 10
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 2 (1947), S. 387-396 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The heats of polymerization of acrylic acid, methyl acrylate, methacrylic acid, and methyl methacrylate have been measured. Values for the heat of polymerization of unstrained polymer molecules have been calculated, and the low heat of polymerization of methyl methacrylate has been attributed to the presence of steric hindrance in the polymer molecule.
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  • 11
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 2 (1947), S. 381-386 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The permeability of vulcanized gutta-percha membranes to gases was determined in relation to the rate of diffusion and solubility. The measurements, as functions of temperature, with four gases were taken below and above the melting point of gutta-percha. The evidence is that the rates of permeation and diffusion increase sharply at approximately 45°C., due to melting of the gutta-percha. In the same way, although to a lesser degree, the solubility of the gas likewise increases at the melting point. The activation energies of permeation and diffusion with the heat of solution were computed from the temperature function of those quantities. It follows from the results that crystallization of the elastomer reduces the gas-solubility, the diffusivity, and the permeability - and increases the activation energy of diffusion. The interpretation of this high activation energy of diffusion is that, because of the crystallization, the macromolecules of the membrane adhere so firmly that greater energy is required to admit the gas molecules.
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  • 12
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A description is given of the preparation, birefringence, and swelling capacity of a series of microscopically homogeneous, partially acetylated cellulose model filaments with an acetyl content varying from 0 to 2.3 acetyl groups per glucose residue, and obtained either by acetylation or by deacetylation. A higher degree of acetylation of these artificial fibers could not be attained without destruction of the fiber. The same holds true for native ramie fibers. The swelling was studied in water, acetone, and methanol. The degree of swelling of the filaments plotted against acetyl content yields entirely different curves for the acetylation and the deacetylation series. These curves can be readily explained by the hypothesis that the intercrystalline (so-called amorphous) portion of the fiber substance is more accessible to the esterification and saponification reactions and is affected earlier than the crystalline portion. The birefringence of the acetylation series shows but a small - although apparently real - difference from that of the saponification series.
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  • 13
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 2 (1947), S. 412-419 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Multi-ingredient polymeric amides have been prepared by the condensation, under amide-forming conditions of various combinations and ratios of components comprising hexamethylenediammonium adipate, hexamethylenediammonium sebacate, and ∊-aminocaproic acid or ∊-caprolactam. The physical properties of the investigated linear polymeric amides range, depending upon the polymer components and the proportions employed, from high-softening, stiff, and difficulty soluble compositions to relatively low-softening, pliable, and easily soluble polymers.
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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 discussion is offered of the x-ray patterns of partially acetylated and saponified cellulose model filaments with varying acetyl contents. They are substantially in conformity with the swelling experiments previously described in Part I (page 397) of this paper. (1) In nonrecrystallized filaments, chemical reaction takes place in the crystallites and the intercrystalline regions from the very beginning of the experiment. The rate of chemical conversion, however, is larger in the latter. (2) Acetylation of the hydrate cellulose crystallites results in a gradual increase in the (101) spacing, A0; the A3 and A4 reflections [corresponding to (101) and (002), respectively] remain unimpaired up to a gross acetyl content of at least 1.5 acetyl groups per glucose residue. (3) Maximally acetylated filaments containing 2.3 acetyl groups per glucose residue may be recrystallized by heating in methanol or ethanol. The diagram of the recrystallized product is identical with the pattern of cellulose triacetate II. With about halfway acetylated or saponified products, recrystallization is not realizable by means of a heating process in water or methanol. (4) Enhanced degree of local order as the result of previous recrystallization of maximally acetylated products produces a more pronounced difference in rate of saponification between the “crystalline” and “amorphous” fiber portions.
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  • 15
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 2 (1947), S. 420-431 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    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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  • 16
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 2 (1947), S. 447-448 
    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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  • 17
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 2 (1947), S. 432-446 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Potentiometric titrations of polymethacrylic acid were performed at different concentrations, different molecular weights, and in the presence of neutral salts, as well as in dioxane-water mixtures. It was shown that the pH of the solutions fulfills the relation, pH = pK  -  n log [(1  -  α)/α]. pK and n are independent of the molecular weight and concentration if a suitable activity factor is introduced. The equation is applicable to free acid solutions as well as acid mixtures. Copolymers of the type, polyallyl acetate-maleic acid, show a more complicated curve. The curve is of the “polydibasic” type. Each branch of it fits equation (2) well. The formula is analyzed and is proposed to be the result of the action of the Maxwell-Partington statistical factor, as well as of the decrease in entropy accompanying the stretch of the randomly kinked molecule. This stretch is caused by the repulsive forces between the ionized carboxyl groups. The distribution curves of the various degrees of ionization present, for any pH, are given. The activity correction implies small units of the size of one or two carboxyl groups. The behavior in salt solutions is dependent not only on the activity correction, but also on the salting-out factor. This factor is high in polyvalent salts. The titration curves in dioxane-water mixtures are satisfactorily accounted for by the change in the activity factor with the dielectric constant.
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  • 18
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 2 (1947), S. 449-449 
    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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  • 19
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 2 (1947), S. 449-449 
    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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  • 20
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 2 (1947), S. 449-450 
    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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  • 21
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The inhibition by quinone and the retardation by hydroquinone derivatives of the peroxide-induced polymerization of styrene have been studied. We have examined the end products of benzoyl peroxide at 74°C. in benzene, alone and in the presence of quinone and hydroquinone ethers, and in styrene in benzene, both with and without quinone. Absorption spectra have been obtained after several time intervals for some of these systems and for the benzoyl peroxide-styrene-benzene system, alone and in the presence of alkyl substituted hydroquinones. Consideration of the end products indicates that quinone interferes but little with the normal initiation process, particularly at low (0.0045 M) concentrations. Inhibition appears to result largely from reaction between the inhibitor and newly initiated chains. Quinone is converted to products - some of which are phenolic - which do not absorb in the visible. The phenolic products may react with the peroxide or radicals from it, interfering with the normal initiation reaction. The hydroquinone derivatives, which are retarders for the polymerization, appear to be converted initially to quinonoid products. The reactions in inhibition and retardation are discussed.
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  • 22
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 2 (1947), S. 487-487 
    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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  • 23
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The correlation between structure and properties of elastomers prepared from dienes, natural rubber, gutta-percha, as well as those of some significant derivatives of natural rubber, are discussed. The similar influence exerted by methyl groups on the brittle point, elastic recovery, and permeability to gases is demonstrated and separated from the effect caused by insertion of  - CH2 - CHR -  groups in straight-chain polybutadiene, which takes place during copolymerization or 1,2 addition. The preponderant influence of an unbranched-chain structure on tensile strength at elevated temperatures and in the swollen state is illustrated. Complex compounds with silver nitrate provide further evidence for the particular symmetry of the natural rubber chain: They are rein forcing agents for synthetic elastomers. The brittle points of hydrochlorides from natural rubber, gutta-percha, and polyisoprene are compared with those of polyvinyl compounds. Correlation between the structure of molecular units in a polymeric paraffin derivative and its elasticity is pointed out.
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  • 24
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 2 (1947), S. 544-544 
    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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  • 25
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 2 (1947), S. 546-546 
    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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  • 26
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 2 (1947), S. 547-564 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Part I traces fine structural features of polythene, beginning with the arrangement of carbon atoms disclosed by x-ray diffraction, and including the incorporation of crystalline segments into crystallites, and finally the combination of crystallites and amorphous regions to form spherulites-the largest structural elements of polythene. Attention is called to the frequent occurrence of side chains in the molecules. The structures of spherulitic and cold-drawn polythenes are compared. Part II describes an experimental study of the cold-drawing of polythene which discloses an interesting variant of this process, designated as “redrawing,” in which dimensional changes differ greatly from those of ordinary cold-drawing. On the basis of these observations and structural considerations presented in Part I, a mechanism of cold-drawing as a rheological process is outlined.
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  • 27
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    Hoboken, NJ : Wiley-Blackwell
    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. 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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  • 29
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experimental methods for measuring the mechanical properties of concentrated polymer solutions and other viscoelastic systems under periodically varying stresses are reviewed. These include direct measurements of stress and strain, measurements of response at resonance frequencies determined by the inertia of the apparatus, propagation of waves in extended media, and measurements of resonance vibrations. The conditions for the suitability of each method are discussed, and equations for the interrelation of the various quantities measured are given. Examples are shown to illustrate the fitting of experimental data to the calculated behavior of mechanical models, in order to obtain frequency-independent mechanical constants which can be interpreted in terms of molecular behavior.
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  • 30
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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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  • 31
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    Journal of Polymer Science 2 (1947), S. 623-625 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A substance may have a precipitating action on other dissolved substances. The concentration at which this action becomes apparent depends not only on the chemical nature of the constituents, but also on their molecular weights. In a homologous series the precipitating power increases with increasing molecular weight until it attains a very high value, as in macromolecules. The incompatibility of high polymers, which is manifested at very great dilutions, is due to this increase in the precipitating power with an increase of the molecular weight.
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  • 32
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    Journal of Polymer Science 2 (1947), S. 626-631 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The same point in the space cannot be occupied simultaneously by two molecules. In a solution of rigid rodlike macromolecules, each molecule prevents its neighbors from occupying certain positions, the whole of which form the forbidden angle. Calculation shows that in the case of rigid, filiform molecules, this angle is large even at very low concentrations. Isotropy is not possible at moderate concentrations. The consideration of the forbidden angle is necessary in the study of viscosity, osmotic pressure, flow birefringence, sedimentation, and molecular light scattering. In the solid state, the substance can be put under great tension, and the return to the normal state is extremely slow. This tension accounts for the abnormal solubility of disordered high polymers.
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  • 33
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The orientation of model filaments stretched to various extents in three different states of swelling was investigated by quantitative x-ray analysis before and after drying. The change in orientation upon drying was found to be either very small or zero. This shows that the crystallites do not even approximately follow the rules of affined transformation which would require a very considerable increase in orientation on drying. There must be an entirely different mechanism which prevents the crystallites from being dragged along with the matrix in which they are embedded.
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  • 34
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    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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  • 35
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    Die Makromolekulare Chemie 1 (1947), S. 85-88 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
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  • 36
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    Die Makromolekulare Chemie 1 (1947), S. 70-84 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 37
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    Journal of Polymer Science 2 (1947), S. 1-9 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rubber hydrocarbon irradiated in vacuo is decomposed by ultraviolet light of wave length less than 4000 Å. The rubber very rapidly becomes insoluble, and liberates a gaseous mixture which consists mainly of hydrogen when the irradiation temperature is less than 150°C. The reaction characteristics have been investigated and point to the occurrence of dissociation processes similar to those deduced for comparable simple olefins. When irradiated above 150°C., small but significant amounts of isoprene appear in the volatile product, thereby providing an experimental means of determining the activation energy for the separation of isoprene from a polyisoprene chain terminated by an allyl radical.
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  • 38
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    Journal of Polymer Science 2 (1947), S. 16-20 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The addition of silver nitrate to polymerizable systems containing butadiene can result in increased over-all rates of conversion. When butadiene is the only monomer and a cationic soap is used the addition of silver nitrate causes* a significant decrease in rate. The most active system studied was one which contained butadiene, styrene, a cationic soap, a peroxide, and silver nitrate. Comparison runs in a GR-S type formulation with silver nitrate and potassium ferricyanide indicate that the silver salt is the more effective in producing higher over-all rates of conversion.
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  • 39
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: A close correlation exists between the modifying effect of mercaptans in emulsion copolymerization of butadiene (75 parts) and styrene (25 parts) and mercaptan consumption during the polymerization. A procedure is described for the rapid amperometric titration of mercaptans in latices. Mercaptan disappearance curves (i.e., mercaptan used at various conversions) are given for a series of primary and tertiary mercaptans of widely varying molecular weight and of two secondary mercaptans. The consumption of (and modification by) primary mercaptans is affected to a much greater extent by the molecular weight of the mercaptan than that of tertiary mercaptans. The consumption of pure and of commercial n-dodecyl mercaptan is greatly affected by the mode and rate of agitation during the polymerization, manner of preparation of the charge (preformed soap and soap “in situ,” separate emulsification of the modifier), dilution of the monomers with inert organic solvents, excess of free caustic in the charge, amount and kind of emulsifier, and the presence of substances which from complexes with the mercaptan. The consumption of tertiary dodecyl mercaptan is not affected by these variables. The difference in behavior between the two mercaptans is interpreted as a faster rate of solubilization into the locus of the reaction of tertiary mercaptans than of primary mercaptans of the same molecular weight. The disappearance curve of a mercaptan from a mixture of two mercaptans remains unaffected by the presence of the other mercaptan. At the same conversion the consumption of a mercaptan increases with decreasing temperature. Disappearance of mercaptan during the polymerization as a result of nonmodifying reactions is discussed.
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  • 40
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    Journal of Polymer Science 2 (1947), S. 90-100 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The phase separation in solutions of high polymers in the same solvent (technically known as incompatibility) has been studied for fourteen high polymers (cellulose, vinyl, and acrylic derivatives) dissolved in thirteen solvents. The influence of solvent, concentration, molecular weight and constitution of the macromolecules has been studied for 78 mixtures: the results are represented in triangular diagrams. Incompatibility appears to be the normal situation, compatibility the exception. Moreover, in cetain cases the exception may be only apparent. Phase separation is discussed in its relation to osmotic pressure, solubility, and the isomorphism of the molecules. Phase separation furnishes new means - useful at leat for technical research - of measuring the molecular weight of macromolecules. It is a simple and rapid procedure.
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  • 41
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
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    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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  • 42
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    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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  • 43
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    Journal of Polymer Science 2 (1947), S. 109-109 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
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  • 44
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    Journal of Polymer Science 2 (1947), S. 111-112 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
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  • 45
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    Journal of Polymer Science 2 (1947), S. 115-120 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: For satisfactory performance in vinyl chloride-acetate resins, plasticizer must be compatible with the resin in a wide range of concentration. Low volatility low rates of extraction by oil and water, and good chemical stability are necessary in most applications. In special applications good electrical properties, low flammability, preservation of compound flexibility at low temperatures, and freedom from odor and taste are also required. Physical test methods, suitable for the evaluation of plasticizers, are briefly described.
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  • 46
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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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  • 47
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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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  • 48
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    Notes: A procedure is given for the determination of the external double bonds in synthetic rubbers. The method is based on the difference in the rates of reaction of perbenzoic acid with internal and with external double bonds. The principles of the interpretation of the analytical data are discussed. Calibration curves for use in the analysis of butadiene and isoprene polymers are given. The procedure is also applicable to the analysis of a mixture of two compounds, one of which contains an external double bond and the other an internal double bond. Data are given for the analysis of mixtures of oleic acid and undecylenic acid.
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  • 49
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    Journal of Polymer Science 2 (1947), S. 229-245 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A review of theoretical progress in copolymerization has shown that the results of previous authors are consistent and equivalent. A general scheme of copolymerization has been stated and its kinetic consequences worked out. The rate expressions have been derived for percentage polymerization against time, and initial rate against initial monomer concentration. Some experimental considerations have been given. The advantages of photochemical technique have been stressed, physical means of following the reaction outlined, and new methods of determining σ and μ described. Means of verifying the kinetics have been suggested, in particular the obtaining of the individual velocity constants. It is important to note in this connection, that further experiments to determine the lifetime of the growing polymer chain are not required.
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  • 50
    ISSN: 0022-3832
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Emulsion polybutadiene and emulsion copolymers of butadiene and styrene (e.g., GR-S) contain about 20% external double bonds. A systematic study has been made of the effects of temperature, type of “catalyst,” percentage conversion, microgel formation, and varying styrene content of emulsion copolymers of butadiene and styrene. None of these variables affects the amount of external double bonds. Copolymers of butadiene with styrene and a small amount of acrylonitrile, and of butadiene with various monochlorostyrenes and dichlorostyrene, all prepared by emulsion polymerization, were found to contain the same amount of external double bonds. Emulsion polyisoprene and the emulsion copolymers of isoprene and styrene (75:25) were found to contain only 13 and 5%, respectively, external double bonds. Polybutadiene, butadiene - styrene copolymer, and polyisoprene, all prepared by sodium - catalyzed, bulk polymerization at 50°C., contain 50-60% external double bonds. The amount of external double bonds in sodium polybutadiene is strongly dependent on temperature of polymerization. More external double bonds are formed at low temperatures than at high temperatures. The amount of external double bonds in sodium butadiene - styrene copolymer and in sodium polyisoprene is nearly independent of temperature in the range 30-50°C. A sample of sodium polyisoprene was found to contain 36% internal double bonds and 64°C external double bonds. From an analysis of the reaction - rate curve it was concluded that approximately 40% (absolute percentage) of the external double bonds were formed by 3,4 addition and 24% by 1,2 addition. The rates of reaction of the cis - and trans - forms of natural rubber are very nearly the same, the cis - form reacting slightly more rapidly.
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    Journal of Polymer Science 2 (1947), S. 246-254 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A mechanism is presented which shows how terpenes and related compounds, some of which are found associated with trans - polyisoprene in nature, may be expected to be formed by a radical chain oxidative degradation of trans - polyisoprene.
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    Journal of Polymer Science 2 (1947), S. 255-256 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
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    Journal of Polymer Science 2 (1947), S. 256-256 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
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  • 54
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the emulsion polymerization of styrene are developed on the basis of the Harkins' theory of reaction loci. Only that portion of the reaction is considered in which essentially no polymer nuclei are formed. Agreement is obtained between experiment and theory when the reaction in the monomer-polymer particle is considered three-halves order with respect to monomer. This treatment is further substantiated by the fact that the concentration of monomer in the polymer, when a separate monomer phase exists, is correctly predicted by the kinetic theory. The activation energy for the polymerization of styrene in the monomer-polymer particle is calculated as 22,600 calories per mole. A dilatometer for the precise determination of monomer conversion rates in emulsion polymerization is described.
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    Journal of Polymer Science 2 (1947), S. 275-280 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Tetrachlorophthalic anhydride (TCPA) was reacted with cellulose diacetate and with cellulose diethyl ether in dioxane solution to produce esters with rather low tetrachlorophthalyl contents. Phthalic anhydride was found to be considerably more reactive than was TCPA with these cellulose derivatives, especially if pyridine was used as the reaction solvent. Acylations could not be executed with TCPA in the presence of pyridine as solvent, however, because this material decomposed the anhydride, removing chlorine from it. The TCPA derivatives were more limited in solubility than were the corresponding esters made from phthalic anhydride.
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    Journal of Polymer Science 2 (1947), S. 263-274 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In this paper experimentally determined values are reported for the thermal diffusivity (k) of various rubberlike polymers. Corresponding values of the thermal conductivity (W) can be computed from the well-known relationship, W = kpcp, where p and cp denote the density and specific heat at constant pressure of the composition. Measurements were made on (a) pure gum stocks prepared with natural rubber, Butyl (GR-I), Perbunan 18, Perbunan 26, Perbunan 35, Buna S (GR-S), polybutadiene, neoprene GN, polyisoprene, Silastic 160, and Silastic 180; (b) pure gum stocks of the first five rubbers listed under (a) containing in addition 20 parts of a hydrocarbon softener (Bardol), based on 100 parts by weight of the polymer; and (c) the Bardol stocks containing in addition 54 parts of carbon black (Kosmobile 66). From measurements of the rate of change of temperature within a rubber sphere suddenly subjected to a change in its surface temperature, it was found possible to determine the dependence of k on temperature. A satisfactory definition of the “mean” temperature of a sphere under these conditions is described. In a discussion of the effect of chemical composition and structure on heat conduction, the bearing of hindered rotation, cross linking and branching and interatomic bond strength on the results is pointed out. Values are derived for certain other properties of some of the polymers, including their characteristic Debye temperatures, specific heats at constant volume, flexibility of the main valence chains, compressibilities, and sound velocities.
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    Journal of Polymer Science 2 (1947), S. 281-289 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This paper is the first part of a review on some recent advances in pectin chemistry. Part I reviews recent work on the constitution and structure of pectin, the characterization of pectin, x-ray diffraction studies on sodium pectate, and the acid dissociation of pectinic acids.
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    Journal of Polymer Science 2 (1947), S. 290-295 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: An attempt has been made in this communication to formulate explicitly the dependence of the frictional coefficients of threadlike molecules in solution upon the centrifugal field applied to them in the usual velocity ultracentrifuges. This quantitative treatment, using the Kuhn and Kuhn odel for randomly coiled free-draining thread molecules, verifies the assumption generally made that the effect considered is negligible. Since the molecular weight of the particles and the magnitude of the centrifugal field applied to them vary inversely with each other, the constant, \documentclass{article}\pagestyle{empty}\begin{document}$\overline {\beta h_0^2 }$\end{document} rarely attains values which are significant, and the effect produced by orientation of the threads is balanced by the effect due to stretching them. Moreover, by a suitable change of parameters, this treatment could be extended to account for the action of other tensile forces acting on thread molecules in solution
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    Journal of Polymer Science 2 (1947), S. 301-305 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
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    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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    Notes: The thermal polymerization of styrene in vacuo has been followed by measuring the change of its magnetic rotatory power. The degree of polymerization was determined from measurements of the refractive index, viscosity, and density. The Verdel constant of the monomer at 25 °C. was found to be 0.0338 minute per gauss per cm.; furthermore, it showed no appreciable change on polymerization. Because of experimental difficulties the measurements could not be made beyond 25% polymerization.
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    Journal of Polymer Science 2 (1947), S. 306-313 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Methods for the preparation of fiber-forming polymeric amides from polymethylene diamines and polymethylene dicarboxylic acids, and the stabilization of these polymers against viscosity changes, have been described. The variation in physical properties, particularly melting points, of the polymeric amides with increasing chain length of the components has been discussed.
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    Journal of Polymer Science 2 (1947), S. 314-317 
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    Keywords: Chemistry ; Polymer and Materials Science
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    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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    Journal of Polymer Science 2 (1947), S. 318-328 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The variation of the x-ray reflection to the interchain separation in sodium pectate has been determined as a function of moisture content. The crystalline regions in sodium pectate have been found to sorb about 24% water (dry basis) at a relative humidity of 95% at 25°C. The sample as a whole under these conditions has a water content of 64%. At high water contents, therefore, a large difference in water content must exist between the crystalline and amorphous regions of sodium pectate. A marked change in degree of crystallinity occurs, as determined by the number and sharpness of the x-ray reflections, at an average water content of about 6% on desorption and on sorption at an average water content of about 14%.
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    Journal of Polymer Science 2 (1947), S. 329-345 
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    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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    Notes: A procedure is described for the rapid sampling of latex during emulsion bottle polymerization. The equipment used consists of a hypodermic needle with holder, an adapter, a balance sensitive to one milligram, and dishes for determination of total solids. The equipment is used in connection with Paracon or Buna N self-sealing caps. The procedure is very simple, rapid, and may be used in obtaining samples for total solids. mercaptan analysis, or gel and viscosity determinations.
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    Journal of Polymer Science 2 (1947), S. 350-351 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Journal of Polymer Science 2 (1947), S. 351-352 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Journal of Polymer Science 2 (1947), S. 352-352 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
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    Journal of Polymer Science 2 (1947), S. 353-353 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Journal of Polymer Science 2 (1947), S. 353-353 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Journal of Polymer Science 2 (1947), S. 36-40 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The usual occurrence of structural units of vinyl polymers in head-to-tail sequence is attributed to the stabilization of the free radical of the growing polymer chain by the monomer substituent(s). Addition at the unsubstituted carbon of the vinyl group reproduces a free radical of lower energy than does addition at the substituted carbon. In at least one instance (vinyl acetate polymerization) a very small percentage of head-to-head addition takes place in spite of this energy difference. These ideas can be extended to polymers of dienes. Here the problem is complicated by the simultaneous occurrence of 1,2 (or 3,4) as well as 1,4 addition. In the case of an unsymmetrical diene monomer such as isoprene it is possible, from detailed examination of the structure of the polymer, to distinguish between preferred addition at carbon atoms 1 and 4 of the monomer.
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  • 72
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
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    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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  • 73
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
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    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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    Journal of Polymer Science 2 (1947), S. 101-106 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: From data in the literature on relative rates of copolymerization it has been possible to evaluate two constants, Q and e, characteristic of an individual monomer, which appear to account satisfactorily for its behavior in copolymerization. The constant Q describes the “general monomer reactivity” and is apparently related to possibilities for stabilization in a radical adduct. The constant e takes account of polar factors influencing copolymerization.
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    Journal of Polymer Science 2 (1947), S. 109-109 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Journal of Polymer Science 2 (1947), S. 109-110 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Journal of Polymer Science 2 (1947), S. 113-114 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Journal of Polymer Science 2 (1947), S. 121-141 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conventional thermodynamic theory of solvent action is briefly reviewed. A mechanistic theory is advanced to supplement the thermodynamic theory. The mechanistic theory views a resin solution as an example of dynamic equilibrium between the tendency of the solvent molecules to solvate the resin and the tendency of the resin macromolecules to unite with each other in three-dimensional aggregation. A plasticizer, being a nonvolatile solvent, remains in the resin film on evaporation of the solvent and thus opposes, to an extent depending on its concentration and solvent strength, the aggregation of the resin macromolecules. Although the permanence of plasticizers in resinous compositions does not correlate well with the author's measure of the relative solvent strengths of the plasticizers, very satisfactory correlation is obtained between the low-temperature behavior of plasticized films and the temperature dependence of the solvent strength of the plasticizers. Data are presented in support of the contention that a necessary condition for good low-temperature performance in plasticized resinous compositions requires that the plasticizer must show a considerable improvement in solvent strength on cooling.
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    Journal of Polymer Science 2 (1947), S. 157-177 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This is a review article concerned with the effect of plasticizers on the second-order transition point and related phenomena in high polymers. The second-order transition temperature behavior of plasticized polymers can be described by a linear relationship between the square root of the weight fraction of polymer and the reciprocal transition temperature. For certain temperature regions and plasticizer contents, this is mathematically equivalent to the linear decrease of transition temperature with plasticizer content which is also observed experimentally. This latter result is in accord with Zhurkov's theory of the softening action of solvents, which predicts a linear decrease in softening temperature with solvent content, and no dependence on the nature of the solvent. Neither the second-order transition approach nor Zhurkov's theory permits conclusions about the nature of the plasticizer. However, it is shown empirically that brittle temperature can be represented as a function of the solvent-polymer interaction constant μ by a curve having a maximum at μ ≈ 0.4. Since μ is also the parameter which measures compatibility, it is seen that the efficiency and the compatibility of a plasticizer are intimately related. Moreover, correlation can be made with older observations showing the relation between efficiency and the temperature coefficient of viscosity of the plasticizer.
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  • 80
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The preparation of perbenzoic acid has been investigated in a n attempt to obtain standard solutions of perbenzoic acid suitable for the amlyszk of unsaturated compounds. Some modifiations of the procedure given by Braun for the preparation of a solution of perbenzoic acid in a n organic solvent are recommended. A study has been made of the stability of solutions of perbenzoic acid in chloroform and in benzene. Benzene or benzene-chloroform mixtures are recommended as solvents for perbenzoic acid. Chloroform solutions of perbenzoic acid which do not contain inhibitors for decomposition have been found to be definitely undesirable in analytical work because perbenzoic acid catalyzes the decomposition of chloroform by oxygen. construction Finance Corporation, in connection with the Government Synthetic Rubber Program.
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    Journal of Polymer Science 2 (1947), S. 503-510 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular weight-viscosity relationships for polystyrene are reviewed and it is recommended that the Staudinger relationship be discarded in favor of the conventional modification of it, [η] = KMa. An emulsion-prepared polystyrene was fractionated and the viscosities and osmotic molecular weight determined. The corresponding relationship between the viscosities in butanone and toluene is observed to follow the above equation. A table containing the molecular weight-viscosity relationships for polymers is appended.
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    Notes: The emulsion polymerizations of butadiene and styrene and of butadiene alone have been studied at temperature of 90-160°. The effects of changes in catalysts, modifiers, times of polymerization, and other variables have been investigated. The rate of polymerization at 110° is markedly increased over that at 50° and the final product is a less modified and less processable polymer. However, the standard evaluation and road tests indicate this polymer may be a useful one.
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    Journal of Polymer Science 2 (1947), S. 487-487 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Journal of Polymer Science 2 (1947), S. 451-462 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The tensile properties of a range of pure gum natural rubbers has been reviewed, and it has been shown that their principal features can be understood on the assumption that the tensile strength measured in a given test depends directly on the amount of crystallization at break. The most important single factor in determining tensile strength is the degree of cross linking. Cross linking is only needed in order to prevent plastic flow, thus permitting the molecules to be aligned by stretching, and hence to crystallize. A very highly cross-linked rubber is weak because the load required to stretch it is so high, that the rubber is broken before the elongation becomes large enough to produce crystallization. In general, vulcanization also involves reactions, e.g., the combination of sulfur with the rubber, which inhibit crystallization by producing structural modifications of the rubber. These reduce the tensile strength, especially when the degree of cross linking is large. These ideas readily explain the effects of swelling and of the temperature of test. They are also used in a brief discussion of the phenomena of overcure, reversion, and aging.
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    Journal of Polymer Science 2 (1947), S. 542-543 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
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  • 86
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: The chemical reactivity of vinyl and diene polymers manifested during aging and degradation is similar to the reactivity manifested during polymerization; namely, the activated intermediates are radicals and the reaction proceeds by a chain mechanism. A discussion of the possible types of aggregative and disaggregative processes involved in aging is presented. On the basis that polymerization and degradation occur by means of the same radical mechanism, experimental evidence is given to indicate that under certain conditions both reactions may occur simultaneously. Viscosity changes of solutions of mono- and polystyrene and methyl methacrylate were studied under varying conditions of heat, oxygen, catalysts, light, and photosensitizers. An analysis of the concurrent aggregative and disaggregative reactions involved in aging may be obtained by isolating one reaction from the other, either by various physical methods, such as intermittent and continuous stress relaxation, or by such classical methods as sol-gel determinations and aging in solution. A comparative study of the rate of oxygen absorption of a large number of polymer types was undertaken to evaluate the factors affecting oxidation. Evidence is presented to show that these factors may be specified by the following: (1) chemical structure of the polymeric material, (2) presence of antioxidants, and (3) compounding and vulcanization. The oxidizability of polymeric materials was also studied in a circulating oxygen absorption apparatus in order to determine the effect of evolved, gaseous oxidation products. A preliminary study of the effect of light on the aging of butyl and GR-S rubber as measured by oxygen absorption and stress relaxation is presented.
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    Journal of Polymer Science 2 (1947), S. 545-545 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Journal of Polymer Science 2 (1947), S. 544-545 
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    Journal of Polymer Science 2 (1947), S. 545-546 
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    Die Makromolekulare Chemie 1 (1947), S. 36-43 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Höhermolekulare Polyoxyundecansäuren vom osmotischen Molekulargewicht über 10000 haben verzweigte Makromoleküle, da das Endgruppenmolekulargewicht, bestimmt aus dem Carboxylgehalt, niedriger ist als das osmotische Molekulargewicht und das andere Endgruppenmolekulargewicht.Das viskosimetrische Molekulargewicht dieser verzweigten Polyester ist ebenfalls geringer als das osmotische Molekulargewicht.Werden die Polyester bei Temperaturen über 200° hergestellt, so treten sekundäre Veränderungen unter Abspaltung von Endgruppen ein.
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    Die Makromolekulare Chemie 1 (1947), S. 94-105 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Eine größere Anzahl von Stoffen wird auf ihre polymerisationshemmende Wirkung hin untersucht, indem ihr Einfluß auf die Geschwindigkeit der Polymerisation und den Polymerisationsgrad des entstehenden Produktes bestimmt wird. Die Messungen erlauben es, die Inhibitoren in 4 Klassen einzuteilen, je nachdem welchen Teilvorgang der Polymerisation sie beeinflussen. Gemeinsam mit Professor G. Wittig wird die Frage untersucht, ob Antioxydantien immer als Polymerisationsinhibitoren wirken. Es zeigt sich, daß alle untersuchten Polymerisationsinhibitoren auch die Autoxydation hemmen, daß aber viele Antioxydantien auf die Polymerisation keinen Einfluß haben.
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    Die Makromolekulare Chemie 1 (1947), S. 89-93 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
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    Die Makromolekulare Chemie 1 (1947), S. 60-69 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Viskosefasern mit einem Polymerisationsgrad über 1000 haben nicht die gleichen günstigen Eigenschaften wie Baumwolle vom gleichen Polymerisationsgrad. Für die guten Eigenschaften der Baumwollfaser ist also nicht nur die Länge der Fadenmoleküle von Einfluß, sondern auch ihre besondere Lagerung in der gewachsenen Faser. Dies wird durch Vergleich von nativen und regenerierten Baumwollnitratfasern nachgewiesen. Der Unterschied in der Löslichkeit von nativen und regenerierten Celluloseacetaten wird ebenfalls mit der besonderen Anordnung der Fadenmoleküle in nativen Fasern in Zusammenhang gebracht.
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    Die Makromolekulare Chemie 1 (1947), S. 158-163 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Durch elektronenmikroskopische Untersuchungen wird der Einfluß des Polyineri-salionsgrades und der Orientierutg der Cellulosemoleküle auf die fibriänre Aufspaltung von Kunstfasern nach nasser Mahlung in der Kugelmühle sowie hydrolytischem Abbau geprüft. Dabei wird festgestellt, daß die Erhühung des Polymerisationsgrades allein ohne Einfluß auf die Art der Aufspaltung ist. Dagegen ruft eine Verbesserung der Orientieruüg der Makrornoleküle durch Verstrecküng im Fällungsbad die Bildung feiner glaeer Fibrillen hervor, wie man sie bisher nur bei netiven Fasern kannte. Eine nachträgliche Verslrcckung fertiger Fasern bewirkt nur eine Orientierung im äußeren Mantel und führt nicht zu ciner Fihrillenbildung. Eine vollständige Nachahmung der nativen Struktur ist jedoch auch durch diese Melhode nicht möglich; denn nach hydrolytischem Ahbau kommt es nicht zur Bildung von Fibrillmahschnitten, die bei gewachsenen Fasern als typische Strukturelemente gefunden wurden, da bei der Ausfällung die Lockerstellen der Cellulosemoleküle nicht in gleichen Ebenen liegen, also kein „Langperiodengitler“ entstehl.
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    Die Makromolekulare Chemie 1 (1947), S. 106-139 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Die Polymerisation des Methacrylsäuremethylesters verläuft bis zu einem Umsatz von etwa 20% stationär (1. Phase). Darauf steigt die Reaktionsgeschwindigkeit unter isothermen Bedingungen bis auf etwa den 70 fachen Betrag an (2. Phase). Bei Annäherung an 100% tritt eine Hemmung der Reaktion ein, derart daß ein bestimmter Anteil des Ausgangsmaterials (je nach Temperatur 2 bis 15%) nicht mit umgesetzt wird (3. Phase). Der isotherme Reaktionsverlauf kann nur unter ziemlich extremen Bedingungen, die wir bei unseren Versuchen einhielten, verwirklicht werden. Bei nichtisothermem Verlauf ist die Reaktionsbeschleunigung außerordent lich viel stärker, da dann die kinetisch bedingte Reaktionsbeschleunigung in eine Wärmeexplosion übergeht.Für die 1. Phase wird ein früher für das Styrol und den Methacrylsäureester aufgestellter Reaktionsmechanismus bestätigt. Einige Reaktionskonstanten könuen auf Grund einer verbesserten Versuchsmethodik präzisiert werden. Der Lettenabbruch besteht in einer Reaktion zweier wachsender Ketten miteinander.In der 2. Phase wird die Diffusionsgeschwindigkeit der im Wachstum befindlichen Ketten durch das bereits entstandene Polymere stark herabgesetzt und dadurch der Kettenabbruch in zunehmendem Maße gehemmt. Das Molekulargewicht der entstehenden Polymeren steigt hierdurch stark an und ebenso die Reaktionsgeschwindigkeit. Im Maximum treten reaktionskinetische Kettenlangen von mehr als 500 000 auf. Eine Reaktionskette läuft dann über 15 bis 20 Makromoleküle.Die Reaktionshemmung in der 3. Phase kommt dadurch zustande, daß das noch nicht umgesetzte Monomere von der polymeren Substanz durch van der Waalssche Kräfte gebunden und dadurch wahrscheinlich für den Primärakt blockiert wird. Diese Bindung kann durch Temperaturerhöhung oder auch durch ein Lösungsmittel, welches an die Stelle des Monomeren tritt, gelockert werden Es erfolgt dann sofort vollständige Polymerisation bis zu 100%.
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    Die Makromolekulare Chemie 1 (1947), S. 140-157 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Durch systematische Untersuchung der Kettenlängenverteilung in polymerhomologen Reihen von hydrolytisch abgebauten nativen und merzerisierten Ramiecellulosen, durch quantitative Fraktionierungen und vergleichende osmotische und viscosimetrische Messungen wird nachgewiesen, daß bei Polymerisationsgraden zwischen 400 und 500 eine erhebliche Vereinheitlichung der Substanz erfolgt. ähnlich wie bei der Baumwollcellulose2 wird aus dieser Tatsache auf das Vorhandensein periodisch im Abstand von etwa 500 Glucoseresten angeordneter schneller spaltender Bindungen in den Molekülen der Ramiecellulose, die nativ mit großer Wahrscheinlichkeit einheitlich ist und einen Polymerisationsgrad von ca. 3000 besitzt, geschlossen. Das Verhältnis der Spaltungsgeschwindigkeiten von normalen β-glucosidischen Bindungen und Lockerstellen läßt sich zu etwa 1 : 5000 abschätzen, ist also erheblich extremer als bei Baumwollcellulosen, bei denen 1 : 1000 gefunden wurde2. Dieses Verhältnis stimmt bei nativen und merzerisierten Produkten trotz der erheblichen Unterschiede in den Spaltungsgeschwindigkeiten überein, ist also von der Faserstruktur unabhängig.
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    Die Makromolekulare Chemie 1 (1947), S. 7-21 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
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    Die Makromolekulare Chemie 1 (1947), S. 44-60 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyaminocapronsäuren vom Molekulargewicht 1500 - 15 000 sind unverzweight, da die beiden Endgruppenmolekulargewichte mit dem viskosimetrischen Molekulargewicht übereinstimmen. Die Gültigkeit des Viskositätsgesetzes wurde bei diesen Polyaminocapronsäuren bis zu einem Molekulargewicht von 20 000 nachgewiesen. Es wird weiter eine Erklärung für die von A. Matthes gefundenen abweichenden Resultate gegeben. Der Zusammenhang zwischen Knickbruchfestigkeit von Fasern und Kettenlänge der Polymaide wird untersucht.
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    Die Makromolekulare Chemie 1 (1947), S. 22-35 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Es werden fünf Polyoxydecansäuren vom osmotischen Molekulargewicht 5000 bis 13 000 beschrieben, bei denen die beiden Endgruppenmolekulargewichte die gleiche Größe haben und die danach unverzweigte Moleküle haben. Da auch das viskosimetrische Molekulargewicht mit diesen Werten übereinstimmt, so wird auf die Gültigkeit des Viskositätsgesetzes geschlossen.Eine Gruppe von anderen Polyoxydecansäuren von gleichem und höherem Molekulargewicht hat verzweigte Moleküle, da das Endgruppenmolekulargewicht, bestimmt aus dem Carboxylgruppengehalt, niedriger ist als das osmotische Molekulargewicht und das andere Endgruppenmolekulargewicht. Die viskosimetrischen Molekulargewichte stimmen bei diesen verzweigten Polyestern nicht mit den Endgruppen molekulargewichten überein.Die Fasern aus unverzweigten und verzweigten Polyestern zeigen bemerkenswerte Unterschiede in der Festigkeit.
    Additional Material: 12 Tab.
    Type of Medium: Electronic Resource
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