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  • Articles: DFG German National Licenses  (4,396)
  • 1970-1974  (2,547)
  • 1965-1969  (1,849)
  • 1890-1899
  • Physics  (4,396)
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  • Articles: DFG German National Licenses  (4,396)
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Years
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  • 201
    Electronic Resource
    Electronic Resource
    The effect of densification on the mechanical properties of amorphous glassy polymers (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1857-1864 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Four polymers, viz. polystyrene, polycarbonate, poly(methyl methacrylate), and poly-(vinyl chloride), were cooled from the melt to room temperature under hydrostatic pressures of 30 and 1000 atm. Cooling under high pressure increased the density by 0.4-0.6%, and the effect of this has been examined for the torsional creep properties, the dynamic properties at 1 Hz, the Charpy impact strength, the thermal expansivity, and the torsional yield stress. It turned out that, in general, densification affects the thermomechanical properties only slightly.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.180120909
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  • 202
    Electronic Resource
    Electronic Resource
    Small-angle x-ray study of deformed bulk polyethylene (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2035-2046 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Scattering by extruded polyethylene films has been used to analyze in detail the small-angle scattering of x-rays by strained spherulitic samples. It is shown that the basic small-angle patterns in spherulitic specimens can be obtained by summing small-angle reflections from films drawn both parallel and normal to the direction of extrusion. The representation of a complex pattern by superposition of simpler reflection makes it possible to calculate local strains in various regions of spherulites in bulk specimens.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.180121006
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  • 203
    Electronic Resource
    Electronic Resource
    Determination of the Flory-Huggins χ parameter, the heat of dilution, and the excess heat capacity of some alkanes in polydimethylsiloxane by gas chromatography (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2065-2074 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The change in standard chemical potential of a number of alkanes on PDMS going from dilute solution to the perfect vapor ΔḠov was measured by gas chromatography over a large range of temperatures. The change in standard chemical potential of the alkane going from the pure liquid to the perfect vapor ΔḠov was calculated from fugacity data. These data were fitted separately to three Taylor's series expansions wherein the (partial) heat capacity of vaporization is zero, constant, and linearly dependent on temperature, respectively. On the basis of statistical and physical arguments it was concluded that the partial excess functions determined by gas chromatography should be described with a temperature-independent partial excess heat capacity.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.180121008
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  • 204
    Electronic Resource
    Electronic Resource
    Relaxations in the transition region of crosslinked polyesters. I. The β relaxation (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2111-2118 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The glass transition region of styrene-crosslinked poly(1,2-propylene phthalate fumarate) was studied using a torsion pendulum. The region was composed of two separate relaxations. The major relaxation was the glass transition of the whole network, while the minor relaxation, at a lower temperature, was ascribed to the polyester segments between the crosslinks. A comparison was made between these relaxations and these observed in related polyester networks.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.180121011
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  • 205
    Electronic Resource
    Electronic Resource
    Time-dependent photocurrents in polyethylene (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2135-2151 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A detailed study of the photocurrents in low-density polyethylene at wavelengths of 350 nm, 300 nm, and 240 nm has confirmed that the current is a linear function of intensity and has established that the observed decrease of current depends on the integrated flux of quanta at the metal-polymer interface, and is independent of intensity and pulse repetition rate. Comparison with electron excitation experiments shows that in the present case, optical ionization occurs within a few angstroms of the interface.Connections between the present results and known photodegradation data are explored, but no firm correlation can be obtained either for the initial “fast transient” or for the “slow transient” which occurs only in the shorter wavelength region. Possible models for hole injection are presented.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.180121013
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  • 206
    Electronic Resource
    Electronic Resource
    Elastic hard polyethylene fibers (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2169-2172 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.180121017
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  • 207
    Electronic Resource
    Electronic Resource
    Dilute solution rheology of flexible macromolecules (bead-rod model) (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2177-2187 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rheological behavior of dilute solutions of flexible macromolecules is studied by means of a freely jointed multiple bead-rod model. The solution of the equations describing the mechanics of the system is obtained by means of a numerical procedure, which applies to arbitrary flow conditions. The case of the transient stress in uniaxial elongational flow is developed in some detail. A comparison with bead-spring models shows both quantitative and qualitative differences which are briefly discussed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.180121101
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  • 208
    Electronic Resource
    Electronic Resource
    Cryoscopy on sulfuric acid solutions of a heterocyclic polymer (BBB) and related compounds (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2253-2266 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cryoscopic measurements have been carried out on solutions in sulfuric acid of a heterocyclic polymer, its monomers, and certain of its oligomers. The polymer, BBB, is prepared by the polycondensation of 1,4,5,8-naphthalenetetracarboxylic acid (NTC) with 3,3′-diaminobenzidine (DAB). The results show that the polymer, its oligomers and one of its monomers, DAB, are all extensively protonated in sulfuric acid, whereas its other monomer is not. The degree of protonation appears to be greater for the polymer than for its low molecular weight oligomers.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.180121105
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  • 209
    Electronic Resource
    Electronic Resource
    Simultaneous polymerization and formation of polyacetylene film on the surface of concentrated soluble Ziegler-type catalyst solution (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 11-20 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A direct method of simultaneously polymerizing and forming acetylene monomer to produce uniformly thin films of polyacetylene was investigated in terms of catalyst system, catalyst concentration, and polymerization temperature. The best catalyst was a Ti(OC4H9)4-Al(C2H5)3 system (Al/Ti = 3-4) and the critical concentration was 3 mmole/l. of Ti(OC4H9)4. Below the critical concentration, only a solid or a powder was obtained. The configuration of the polymers obtained depends strongly upon the polymerization temperature. Thus an all-cis polymer was obtained at temperatures lower than -78°C, whereas an all-trans polymer resulted at temperatures higher than 150°C. Observations either in an electron microscope by direct transmission or in a scanning electron microscope showed that the film is composed of an accumulation of fibrils about 200-300 Å in width and of indefinite length.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120102
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  • 210
    Electronic Resource
    Electronic Resource
    Stereochemistry of alternating methacryloyl-L-valine methyl ester-maleic anhydride copolymer (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 57-65 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The stereochemical composition of an alternating methacryloyl-L-valine methyl estermaleic anhydride (L-MAVM/MAn) copolymer which was prepared by the photocopolymerization of L-MAVM and MAn in dioxane at 25°C without initiator was investigated by proton magnetic resonance spectroscopy. The resonance of the ester methyl protons of the L-MAVM unit appeared as three split peaks at 3.65, 3.76, and 3.82 ppm, which could be assigned to those of the coisotactic (di-threo-tri-isotactic), coheterotactic and cosyndiotactic triads, respectively. The triad cotacticity determined according to these assignments indicated that the copolymer was composed predominantly of di-threo-tri-isotactic triad. Similarly PMR spectroscopic investigation of the acryloyl-L-valine methyl ester-maleic anhydride (L-AVM/MAn) copolymer with a 1:1 molar ratio of the monomers showed that the main tactic fraction of the copolymer was also di-threo-tri-isotactic one. Nevertheless, the circular dichroic investigation of the L-AVM/MAn copolymer before and after hydrolysis denied asymmetric induction into the polymer main chain. These results suggest that the propagation step in the photocopolymerization of L-MAVM or L-AVM with MAn proceeds by the trans-trans opening of the complexmer composed of a 1:1 molar ratio of L-MAVM or L-AVM and MAn.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120106
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  • 211
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    Radiation-induced emulsion polymerization of ethylene. II. Effect of potassium myristate concentration and dose rate on the rate of polymerization in connection with polymer properties, kinetics, and mechanism (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 93-103 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radiation-induced emulsion polymerization of ethylene with potassium myristate as an emulsifier was studied in connection with the kinetics and the mechanism. The molecular weight of polymer was relatively low, of the order of 103, when a sufficient amount of emulsifier was used. However, polyethylene gel was produced in the absence of a sufficient amount of emulsifier. The rate of polymerization was proportional to the 0.5 power of dose rate and increased slightly with increasing emulsifier concentration. The rate of seeded polymerization followed a similar trend to that for conventional polymerization. Kinetic analysis of these results suggests that the escape of radicals produced by chain transfer of propagating radical with the emulsifier and the monomer from polymer particles into the aqueous phase plays an important part in the rate of polymerization. The melting temperature and the crystallinity of the polymer significantly decreased with increasing polymerization temperature in the range 40-60°C.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120109
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  • 212
    Electronic Resource
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    Imidization during polymerization of acrylamide (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 133-140 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The spontaneous imidization of acrylamide during polymerization has been studied in three media: benzene, diglyme, and water. The data indicate that neither medium, time, nor temperatures below 140°C cause imidization to occur. The ascription of the low nitrogen found in polyacrylamide by some investigators to imide formation appears to be in error. The low nitrogen is due rather to retained solvent and/or water, for which polyacrylamide has a strong affinity. Imidization may be brought about by strong acids. The solubility of an imidized polyacrylamide decreases with increasing imide content.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120112
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  • 213
    Electronic Resource
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    Reaction of polyamine polymer with molecular iodine via charge-transfer complex formation (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 167-181 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of a Mannich base type-polyamine polymer with iodine (I2) was studied kinetically and thermodynamically in order to clarify the polymer effects in the formation of triiodide ions (I3-). N,N-Dimethyl-p-(4-methylpiperazinomethyl) aniline and 1,4-dimethylpiperazine were used as low molecular weight donor model compounds. Triiodide ions are produced from the polyamine-I2 system immediately after mixing the two-component solutions, while in the systems with I2 and N,N-dimethyl-p-(4-methyl-piperazinomethyl)aniline and 1,4-dimethylpiperazine they are obtained only when relatively high concentrations of both donor and acceptor solutions were mixed. This is explained by the entropic contributions of the polymer chain such as the stacking effect of donor nitrogen atoms, i.e., the increment of local donor concentration around I2 in the reaction field. The relation between the solution behavior of the reaction systems and the rate of formation of I3- ions also supports this kind of polymer effect. The effects of neighboring groups and dielectric constant on the reaction are also discussed.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120115
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  • 214
    Electronic Resource
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    Temperature dependence on the binding of butyl orange by bovine serum albumin (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 191-200 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The binding of 4′-dibutylaminoazobenzene-4-sulfonate anion (butyl orange) by bovine serum albumin has been examined quantitatively by an equilibrium dialysis method at 5, 10, 15, 20, 25, and 35°C. The first binding constants and the thermodynamic parameters for the formation of the first dye anion-protein complex have been calculated. The peculiar temperature dependence of the first binding constant could be observed. That is, the value of the first binding constant increases with increasing temperature until it reaches a maximum value at approximately 18°C and then decreases with raising temperature. Accordingly, this binding process is exothermic above 18°C and is endothermic below 18°C. Near 18°C the process exhibits athermal reaction. From the thermodynamic data obtained, it is evident that the favorable free energy of the binding is accompanied by an entropy gain and that the enthalpies of the binding vary from a positive (unfavorable) value below 18°C to a negative (favorable) one above 18°C. Furthermore an apparent temperature dependence of the thermodynamic functions was observed. That is, ΔF° becomes larger in absolute magnitude as the temperature increases. The positive quantity of ΔS° tends to decrease with increasing temperature. All these facts can be interpreted satisfactorily in terms of hydrophobic interactions between hydrophobic portions of the dye and nonpolar parts of the albumin.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120117
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  • 215
    Electronic Resource
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    Apparatus for observing thermal variations in retardance of birefringent materials (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 241-246 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120122
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  • 216
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    Crystallization-induced reactions of copolymers. IV. Ester-interchange reorganization of poly(ethylene terephthalate-co-2-methylsuccinate) (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1-10 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The application of ester-interchange reactions to the crystallization-induced reorganization of random to block copolymers, which was demonstrated in the previous paper of this series, was followed quantitatively in this investigation. Structural changes based upon dyad compositions in copolyesters of terephthalic acid and 2-methylsuccinic acid with ethylene glycol were determined by high-resolution NMR. Sequence length distributions so calculated were related to the effects of copolymer composition, catalyst concentration, and reaction temperature on the rate of the ordering process and to the effect of structure on crystalline properties.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120101
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  • 217
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    Diffusion into and adsorption of polyethylenimine on porous silica gel (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 29-43 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polyethyleneimine (PEI)-water-silica gel absorption system was used as a model system to investigate the relationship between diffusion into the porous structure, adsorption rate, and molecular weight of the polymer. Three silica gels, Porasil A, B, and and C having a range of characteristic porosity were used as adsorbents. Adsorption of PEI on Porasil C, which has the majority of its pores much larger than the dimensions of the adsorbate molecule, increased initially with increased molecular weight but became nearly constant at higher molecular weight. Little increase in adsorption occurred for this silica gel with increased ionic strength or with increased pH between 9.5 and 10.8. In contrast, adsorption increased sharply with increased ionic strength and for the same pH range on Porasil A. Molecular weight dependence was reversed. Adsorption decreased with increased molecular weight on Porasil A. In this case, the molecular size of PEI investigated was the same as the majority of pore apertures in the adsorbent. Solution environments (i.e., pH and ionic strength) that decrease the size of the PEI molecule and its affinity for the anionic silica gel surface, thus enabling it to more readily diffuse into the smaller porous regions of the adsorbent, are the apparent causes of the very large adsorption increase. Electrostatic repulsion between PEI molecules do not appear greatly to affect adsorption. Similar adsorption behavior has been reported in the literature for the PEI-cellulosic fiber adsorption system. Maximum adsorption on Porasil A occurred at pH 10.8, the same maximum generally reported for adsorption of PEI on cellulosic fibers. In this case, the silica gel (Porasil A) was found to have a pore size distribution and specific surface area of the same magnitude as cellulosic fibers prepared in the expanded state.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120104
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  • 218
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    Radiation-induced emulsion polymerization of ethylene. I. Effect of reaction conditions on the polymerization (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 83-92 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of reaction conditions on the rate of radiation-induced emulsion polymerization of ethylene was studied by use of a 500-ml autoclave. Among various kinds of emulsifiers, a series of potassium salts of fatty acids gave high rates of the polymerization. The polymerization was inhibited by the presence of oxygen, but the rate of polymerization followed by the induction period was not influenced by the initial presence of oxygen. Stirring rate and the monomer: water ratio did not affect the rate of polymerization. The rate of polymerization was maximum at about 80°C, and number-average molecular weight was influenced by the temperature in a similar manner as the rate of polymerization. This suggests that the change of mobility of propagating radical in the polymer particle changes the rate of termination reaction. The rate of polymerization was proportional to the 1.7 power of the reaction pressure.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120108
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  • 219
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    Copolymerization of carbon dioxide with propyleneimine (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 121-131 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Carbon dioxide and propyleneimine were allowed to copolymerize without using any catalyst to give a polyurethane with a carbon dioxide content of 10-35 mole-%. The polymer yield, the specific viscosity, and the content of carbon dioxide in the copolymer increased with increasing polymerization temperature. The infrared spectrum of the copolymer showed the characteristic peak assignable to a cyclic urethane(4-methyl-oxazolidone-2) at 1750 cm-1 as well as the peak characteristic of the urethane linkage at 1700 cm-1. The relative intensity ratio of the former absorption to the latter decreased markedly with increasing polymerization temperature. Propyleneimine did not polymerize at all in the absence of carbon dioxide. Polymerizations were also carried out with the use of various solvents. On the basis of these results, a probable reaction scheme of the copolymerization was proposed.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120111
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  • 220
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    Anionic polymerization initiators containing protected functional groups and functionally terminated diene polymersPresented in part at the Division of Polymer Chemistry, American Chemical Society, August 26-31, 1973, Chicago, Illinois. (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 153-166 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Organolithium reagents substituted with hydroxyl-carrying mixed acetals (i.e., tetra-hydropyranyl and α-ethoxyethyl ethers) have been prepared in high yields and used to polymerize 1,3-butadiene to various acetal-terminated polybutadiene polymers. A method is described for converting acetal-containing polymers into hydroxyl-containing polymers. The polybutadienes have been characterized with regard to endgroup types, quantitative functionalities, molecular weights, molecular weight distributions, and microstructures. Dihydroxyl terminated polymers are prepared anionically in the absence of gel. Such materials are more suitable from the standpoint of f(OH) and M̄w/M̄n for chain extension studies than are prepolymers prepared by radical methods.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120114
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  • 221
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    Titration curves of some structurally and molecularly uniform polynuclear phenolic compounds with additional functional groups (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 211-219 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120119
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  • 222
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    Inorganic coordination polymers. XIV. Chromium(III) phosphinate perfluorocarboxylate polymersFor Part XIII of this series, see Gillman, Nannelli, and Block.1 (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 221-229 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of polymers, {Cr(OH)(OPRR′O)[OOC(CF2)nCF(CF3)2]}x has been prepared and studied. The polymers with R = R′ = C6H5 are soluble in CCl2FCClF2, whereas those with R = CH3 and R′ = C6H5 and with R = R′ = C8H17 are insoluble in all solvents. Attempts to prepare similar materials without hydroxyl groups gave the polymers {Cr(OH)r(OPRR′O)p[OOC(CF2)nCF(CF3)2]q}x with 0 〈 r 〈 1. The latter polymers are much more tractable than the former; however they are also less thermally stable. The perfluoro-carboxylate groups in these materials can either be chelating or bridging, depending on the other ligands present.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120120
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  • 223
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    Note on the kinetics of methyl methacrylate emulsion polymerization (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 251-254 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120124
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  • 224
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    High temperature polymers. I. - Sulfone ether diamines as intermediates for tractable high temperature polymers (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 565-573 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A useful synthesis of a series of new aromatic sulfone ether diamines, H2NC6H4O\documentclass{article}\pagestyle{empty}\begin{document}$\hbox{---}\hskip-5pt[\ {\rm C}_{\rm 2} {\rm H}_{\rm 4} {\rm SO}_{\rm 2} {\rm C}_{\rm 6} {\rm H}_{\rm 4} \hbox{--} {\rm ORO}\hbox{---}\hskip-5pt ]_n {\rm OC}_{\rm 6} {\rm H}_{\rm 4} {\rm SO}_{\rm 2} {\rm C}_{\rm 6} {\rm H}_{\rm 4} \hbox{---} {\rm OC}_{\rm 6} {\rm H}_{\rm 4} {\rm NH}_{\rm 2} $\end{document}, where n = 0, 1, 2…, which increases the tractability of polyimides, polyamide-imides, and polyamides, was developed. These diamines were prepared by condensing various proportions of sodium p-aminophenate, sodium bisphenates, and dichlorodiphenyl sulfone. The synthetic procedures are now refined to the point where simply coagulating these diamines into water yields high purity polymer-grade sulfone ether diamines. The latter have good tractability; and in some cases, it is possible to extrude and injection-mold these high temperature polymers.
    Additional Material: 4 Tab.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120308
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  • 225
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    High temperature polymers. III. Diphenyl sulfone-based polyamide-imides (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 589-601 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High temperature thermoplastic polyamide-imides were prepared from a new series of aromatic diamines containing the diphenylsulfone unit and alternatively, oxydiphenyl and diphenylisopropylidene units. The polymers were prepared in their completely imidized form by using a facile in situ chemical imidization reaction which offers several advantages over the conventional thermal imidization process. The sulfone-based polyamide-imides exhibited an excellent combination of moldability, thermal stability, mechanical properties and solvent resistance. Analysis of the properties of these polymers in terms of structural variations permits a useful correlation of the effect of various structural units on performance. The polar diphenyl sulfone and amide-imide units increase the glass transition temperature and improve solvent resistance while the oxydiphenyl and diphenylisopropylidene units improve thermoplasticity. Sulfone ether diamine polyamide-imide (VI) offers the best combination of high temperature performance and moldability.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120310
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  • 226
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    Polymerization of vinyl acetate retarded by 4-methyl-2,6-di-tert-butylphenol: Kinetic and ESR studies (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 347-356 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 4-Methyl-2,6-di-tert-butylphenol strongly retards the free radical polymerization of vinyl acetate initiated by azobisisobutyronitrile. The chain transfer constant, estimated from rate data, is 0.020 ± 0.004 at 35°C and does not vary significantly with temperature. Molecular weight data lead to transfer constants of 0.023, 0.020, and 0.024 at 35, 45, and 55°C, respectively. A mean kinetic isotope effect of 9.8 ± 1.0 is observed for the phenol deuterated at the OH group, showing that the main attack of poly(vinyl acetate) radicals on the phenol involves hydrogen abstraction from this group. The activation energy for hydrogen abstraction is estimated to be 7.8 kcal/mole, and the rate constant at 50°C is 160 ± 40 1./mole-sec. The stationary concentration of 4-methyl-2,6-di-tert-butylphenoxyl in the polymerization mixture is proportional to the phenol concentration and is independent of the initiator concentration, as shown by electron spin resonance studies. Cross termination of poly(vinyl acetate) and phenoxy radicals occurs to a greater extent than mutual termination of these radicals. The rate constant for cross termination is close to 1 × 108 1./mole-sec at 50°C; the activation energy for cross termination is 2.9 ± 1.3 kcal/mole.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120208
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  • 227
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    Kinetics of radiation-induced bulk polymerization of vinyl chloride in the temperature range of -50 to 90°c (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 411-432 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetic investigations on the bulk polymerization of vinyl chloride initiated by exposure to 60Co γ-rays were carried out in the temperature range of -50 to 90°C at dose rates varying from 0.15 to 50 rad/c. Some polymerization runs were also carried out in a centrifugal field. As generally reported for this polymerization system, in which the polymer is insoluble in the monomer, the polymerization rate was found to change as a function of the amount of the polymer formed in a special fashion. This particular function has been shown to be greatly influenced by the polymerization temperature and to be independent of the rate of initiation, or, more rigorously, of the dose rate. Thus, at any given temperature the equation of the polymerization conversion rate could be written in the form of the product of two separate functions, one for the polymerization conversion and the other for the dose rate. While for the latter the results gave an essentially square-root dependence on dose rate as is normally found for homogeneous polymerization, the former has been discussed in the terms of recently advanced kinetic schemes, based on a two-phase polymerization model. The kinetic parameters found in this work are in agreement with previous authors' data.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120213
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  • 228
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    Synthesis of polymers by using divalent metal salts of mono(hydroxyethyl) phthalate: Metal-containing polyurethane-ureas (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 469-481 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of metal-containing polyurethane-ureas containing ionic links in the main chain was synthesized by the polyaddition reaction of hexamethylene diisocyanate with mixtures of metal salts of mono(hydroxyethyl) phthalate and bisureas containing two hydroxyl groups which were obtained from monoethanolamine and diisocyanates. The polyurethane-ureas obtained were generally yellowish powders or solids. Close agreement between observed and calculated values of metal content of the metal-containing polyurethane-ureas was obtained. The viscosities (in dimethylformamide) of polyurethane-ureas decreased markedly with increase of metal content. Moreover, the decomposition temperatures were lowered a little by introducing metals into the polyurethane-ureas. Dimethylformamide, m-cresol, and dimethyl sulfoxide were comparatively good solvents for the metal-containing polyurethane-ureas; however, the polymers were insoluble in all other solvents.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120217
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  • 229
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    Metal compounds in free-radical processes. II. Interaction of copper (II) chelates of N-alkylnorephedrines with peroxides and 2,2′-diphenyl-1-picrylhydrazyl (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 513-519 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of the copper (II) chelates of norephedrine (I), N-methylnorephedrine (II), N-ethylnorephedrine (III), and N-n-butylnorephedrine (IV) with benzoyl peroxide, cumene hydroperoxide, and 2,2′-diphenyl-1-picrylhydrazyl have been studied. Only the chelates of N-alkyl-substituted norephedrines enter into the reactions with free radicals, while their reactivity increases with the length of the alkyl substituent in the amino group of the ligand. The decomposition of cumene hydroperoxide was catalyzed by all four chelates; the catalytic efficiency increases in the order I〈II〈III 〈 IV.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120303
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  • 230
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    Crosslinked polymers of styrene with 1,3,5-triisopropenylbenzene (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 561-564 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Crosslinked polymers of improved properties compared to those of pure polystyrene, are obtained by the thermal or radical copolymerization of styrene with 1,3,5-triisopropenylbenzene. The copolymers are transparent glassy solids, practically insoluble in most organic solvents and easily machineable. They decompose at about 350°C. Copolymers containing 5-30% of 1,3,5-triisopropenylbenzene exhibit the better properties.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120307
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  • 231
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    Synthesis and thermal properties of a new class of high-temperature polyamides from hexahydrobenzodipyrrolePaper presented at the IUPAC International Symposium on Macromolecules, Aberdeen, Scotland, September 10, 1973. (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 761-770 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of polyamides was synthesized by the interfacial polycondensation of 1,2,3,5,6,7-hexahydrobenzo [1,2-c:4,5-c′] dipyrrole with isophthalic, terephthalic, oxydibenzoic, sebacic and adipic acid chlorides. High molecular weight polymers with inherent viscosities ranging from 0.4 to 2.3 dl/g were obtained. Polymerization with isophthaloyl chloride gave the highest molecular weight polymer in this series. These polyamides melt between 350°C and 475°C, depending on structural differences as determined by differential scanning calorimetry (DSC). Rapid weight loss in these polymers was observed in the range of 350-400°C under thermogravimetric analysis in a nitrogen atmosphere. All these polyamides are susceptible to photooxidative degradation. The results were compared with Nomex polymer poly(1,3-phenylene isophthalamide).
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120406
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    Cationic copolymerization of phenyl propenyl ethers (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 613-626 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ring-substituted phenyl propenyl ethers were found to form homopolymers without any rearrangement by metal halides. Phenyl propenyl ethers were less reactive than the corresponding phenyl vinyl ethers in cationic polymerization. In order to study the electronic effect of a substituent on the reactivity, cis-p-Cl,p-CH3, and p-CH3O-phenyl propenyl ethers were copolymerized with phenyl propenyl ether in methylene chloride at -78°C with stannic chloride-trichloroacetic acid, and their 1H- and 13C-NMR spectra were measured. The reaction constant ρ against Hammett σp was -2.1. The cis-phenyl propenyl ethers were slightly more reactive than the corresponding trans isomers. On the other hand, an o-methyl group decreased the reactivity of phenyl propenyl ether. The low reactivity of o-methyl phenyl propenyl ether was attributed to the steric hindrance between the propagating carbocation and the monomer.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120312
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    Preparation of new reactive methylene monomers (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 985-992 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acryloylacetone, methacryloylacetone, and related monomers have been synthesized by using cyclopentadiene as a blocking agent during the Claisen condensation.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120506
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  • 234
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    Stereoelective polymerization of tert-butyl thiirane (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1001-1010 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization in bulk of racemic tert-butyl thiirane with a chiral initiator resulting from the reaction between diethylzinc and (—)3,3-dimethyl-1,2-butanediol produces an optically active polymer by preferential consumption of R enantiomer. The unreacted monomer is enriched in S enantiomer. The relative rate r of consumption of R enantiomer versus S enantiomer is as high as 2.8. Obtained polymer could be separated into two crystalline fractions: an optically active fraction, formed from regular sequences of R type enantiomeric units, and an optically inactive fraction which corresponds to a racemate. Experimental results are consistent with a stereospecific mechanism of addition, the two enantiomers being chosen by two different type of sites. The stereoelective process is due to an unequal number of these two types of sites.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120508
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  • 235
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    New routes for copolymerization of carbon monoxide with styrene or vinyl chloride and photodegradation of these copolymers in solutions (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1041-1048 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New routes for copolymerization of carbon monoxide with styrene or vinyl chloride were found by emulsion polymerization (nonionic or ionic emulsifier). These procedures yielded copolymers containing carbonyl groups even at high conversion. These carbonyl-containing polyketones were photoirradiated in solvent. In carbon monoxide - styrene copolymer of high molecular weight, the viscosity change produced by photoirradiation was especially remarkable, while in carbon monoxide - vinyl chloride copolymer no pronounced change in viscosity was observed, even at high contents of carbonyl group.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120511
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    Molecular chain conformation and crystallite structure of cellulose. I. Fine structure of rayon fibersPortions of this paper have been presented by the authors at the 19th, 20th, and 21st annual meetings of the High Polymer Society in Japan, Tokyo, 1970, 1971, and 1972. (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1065-1087 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A most reasonable folded-chain model for the fine structure of rayons (cellulose II) has been developed through experimental work on a theoretical basis. All the materials uniformly gave a levelling-off DP of about 40, equivalent to a length around 200 Å, for cellulose molecule segments at the early stage of heterogeneous acid hydrolysis when the first minor fraction is scarcely dissolved. Measurements by small-angle and wide-angle x-ray scattering put the crystallite length from various rayon fibers at about 200 Å, without exception. A family of GPC chromatograms, furthermore, on the hydrolyzed cellulose exhibited a single peak considered to represent monodispersed materials. These data suggest that clearly divided sections exist within the microfibril along its axis in a regular manner at an interval of about 200 Å. This cannot be explained in terms of the fringed micelle model. On the other hand, the possibility that cellulose II may have a folded-chain conformation has been demonstrated. A single cellulose molecule is essentially folded back and forth in the (101) plane to form a sheetlike structure. Such a structure is the basic unit that can fit perfectly into the unit cell of cellulose II. The cellulose molecule can achieve a fairly sharp U-turn in the (101) plane, with only one glucose unit of in the half-boat conformation. A crystallite consists of a number of sheets held together by secondary forces in the (101) plane. Accordingly, crystallographically, the crystallites are closely packed at the surface of each fold at its longitudinal edges to make up the cellulose microfibril. According to our model, the oxygen atom of the glucosidic link in the fold, where acid hydrolysis would have to take place, protrudes partially from the surface of the crystallite; a pair of atoms at the folds are then facing each other and are therefore, accessible for hydrolysis. This would explain chain scission of cellulose II at these sites in hydrolysis. This folded-chain model is supported further by other experimental evidence.
    Additional Material: 13 Ill.
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    Ion ⇄ ester equilibria in the living cationic polymerization of tetrahydrofuranThis paper was presented in part at the International Symposium on Cationic Polymerization, Rouen, France, 1973. (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1333-1336 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120620
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    Phosphorescence from nylon polymers: Effects of thermal and photochemical oxidation (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1233-1241 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The phosphorescence from the nylon polymers 6, 66, 11, and 12 has been studied from the aspects of excitation and emission wavelength location and of emission lifetime. In contrast to the other nylons, the 66 polymer exhibits two distinct phosphorescence bands, both of which are sensitive to thermal and photochemical oxidation of the polymer. The species responsible for these emissions are concluded to be carbonyl in nature and their role in the complex reactions that occur during thermal and photochemical oxidation of the polymer is discussed.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120609
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  • 239
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    Cyclopolymerization of isoprene with VCl4-AlEt2Br catalyst system (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1257-1262 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Isoprene was polymerized at 30°C with VCl4-AlEt2Br catalyst system in n-hexane. A linear dependence of rate of polymerization on the monomer and catalyst concentrations was found. The overall activation energy was 8.96 kcal/mole. Infrared spectra of polyisoprene showed the presence of cyclic structure, indicating a cationic mechanism of polymerization.
    Additional Material: 7 Ill.
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    Absorption of polymers at the solution-solid interface. XII. Stabilization of dispersed silica by absorbed styrene-methyl methacrylate copolymers (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1269-1290 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ability of styrene-methyl methacrylate copolymers to stabilize silica dispersions has been investigated. Random, block, and graft copolymers covering the entire composition range have been employed in carbon tetrachloride, trichloroethylene, and benzene solutions. Equilibrium sediment volumes and dispersion turbidities provide adequate and concordant estimates of stabilization efficiency. Polystyrene is not adsorbed by precipitated silica from trichloroethylene or benzene and does not stabilize dispersions in these liquids; although adsorbed from carbon tetrachloride, there is no stabilization. Poly(methyl methacrylate) is an efficient dispersion stabilizer, and its performance is independent of molecular weight over a wide range. Random copolymers having styrene contents in excess of ca. 60% do not stabilize in trichloroethylene but do so in carbon tetrachloride, although well adsorbed in both cases. With this major exception, and that of a low-styrene graft copolymer in carbon tetrachloride, copolymers of all structures and compositions stabilize well, better than poly(methyl methacrylate) in the solvents examined. A substantial degree of surface coverage is necessary for optimum stabilization. Subsidiary solution adsorption and layer thickness measurements are also reported.
    Additional Material: 14 Ill.
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    Fractionation of polystyrene by slow freezing of dilute polystyrene solutions in benzene under a small temperature gradient (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1323-1325 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120618
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    Polymerization of N-vinylcarbazole by chlorides and oxychlorides of some group V elements. III. Effect of some transfer and terminating agents on the kinetics (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1337-1343 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120621
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  • 243
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    Investigation of physical state and phase behavior of polyester-imides (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1375-1383 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Changes in properties of linear aromatic heterocyclic polymers of the polyimide class after introduction of ester linkages into their dianhydride component and of the oxygen and sulfur atoms into their diamine component have been studied. Thermomechanical, dilatometric, thermographic characteristics and x-ray diffraction patterns of poly(ester amic acids) and polyester-imides have been investigated. On heating, poly(ester amic acids) and amorphous polyesterimides exhibited a peculiar effect of self-orientation of macromolecules. The x-ray diffraction patterns of unoriented films indicate that they exhibit axial-planar texture with the c axis of macromolecules in the film plane. The formation of the texture is preceded by mutual arrangement of macromolecules, i.e., by a precrystallization process beginning in the amorphous state. Because of this, on heating at temperatures ranging from 200 to 380°C, polyester-imides yield highly crystalline products. Crystallographic parameters of the polymer lattices on x-ray diffraction patterns and dichroism of absorption bands in polarized infrared spectra, the most probable conformations of macromolecules of some polyesterimides are proposed.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120702
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    Polymers having stable radicals. II. Synthesis of nitroxyl polymers from 4-methacryloyl derivatives of 1-hydroxy-2,2,6,6-tetramethylpiperidine (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1407-1420 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymers having stable pendant . radicals were synthesized through their precursor polymers by oxidizing them in air or by H2O2-Na2WO4. Hydrochlorides and sulfates of 4-methacryloylamino- and 4-methacryloyloxy-1-hydroxy-2,2,6,6-tetramethylpiperidines were synthesized as precursor monomers and polymerized by using α,α′-azobisisobutyronitrile under appropriate conditions to precursor polymers of high molecular weight: poly-4-methacryloylamino-/oxy-1-hydroxy-2,2,6,6-tetramethylpiperidinehydrochlorides and sulfates. The precursor polymers were converted to polymers having nitroxyl stable radicals, i.e., poly-4-methacryloylamino-/oxy-2,2,6,6-tetramethylpiperidine-1-oxyls, by oxidation in air or with H2O2-Na2WO4 without any main-chain scission. The structure of the resultant stable radical polymers was determined by infrared, ultraviolet, and ESR spectroscopy. Based on the results of spectroscopic analysis and Kjeldahl analysis, the transformation from precursors to nitroxyl stable radical polymers was found to be quantitative. Investigations on the applicability of polymeric nitroxyl radicals to oxidation-reduction reactions were attempted by means of polarography; the reduction half-wave potential was found to be -1.16 V for the mercury pool.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120705
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    Wetting properties of bis(trifluoromethyl)carbinyl acrylate polymersPresented in part at the 7th International Symposium on Fluorine Chemistry, Santa Cruz, California, July 16-20, 1973. (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1421-1436 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of bis(trifluoromethyl)carbinyl acrylate monomers [Y-C(CF3)2 O—CO—CH=CH2] in which Y is CH3, CH3CH2, CH3CH2CH2, CH3CH2CH2CH2, C6H5, H, F, CF3, N3, CN, and CH3OCH2CH2O, was prepared. Polymers were easily prepared from all of these monomers except where Y = CN, wherein a variety of initiation methods failed to produce high molecular polymer. Wettabilities of the polymer films were examined by means of contact angle measurements by using n-alkane test liquids and water. Values of the dispersion force contribution (γsd) and the polar force contribution (γsp) to the solid surface energy were calculated by employing both geometric and harmonic mean approximations. Values of γsd calculated by either method agreed well with γc (critical surface tension) values determined graphically from contact angle data employing n-alkane test liquids, confirming the suggestion that γc is an approximate measure of the dispersion force contribution to solid surface energy. Values of γsd ranged from 15 dyne/cm (Y = F or CF3) to 25 dyne/cm (Y = C6H5). Values of the polar force contribution to solid surface energy (γsp) varied from 0.6 dyne/cm (Y = CH3CH2CH2CH2) to 3.4 dyne/cm (Y = CH3OCH2CH2O) when calculated by the geometric mean equation. The values of γsp obtained from the harmonic mean equation followed the same trend upon varying substituents, but were larger in value, ranging from 2.9 dyne/cm (Y = CH3CH2CH2CH2) to 7.5 dyne/cm (Y γ CH3OCH2CH2O).
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120706
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  • 246
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    γ-radiolysis of ketone polymers. III. Copolymers of ethylene and carbon monoxide (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1469-1491 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The γ-radiolysis of copolymers of ethylene and carbon monoxide (CO-PE) containing 0-9 wt-% of CO has been studied in the solid phase under vacuum with respect to hydrogen production, scission, and crosslinking. In this regard, the introduction of carbonyl groups into polyethylene increased both the scission and crosslinking efficiency. However, a theoretical statistical treatment for random scission and crosslinking, which was used to calculate G(s) and G(x) yields, predicted gelation with irradiation dose; this was confirmed experimentally. The increased G(x) values are attributed to the localization of absorbed energy in the carbonyl group arising from preferential trapping of thermalized secondary electrons. A stoichiometric balance is shown to be consistent with the reduction of one carbonyl group to a secondary alcohol per excess crosslink observed. The G(H2) yield is reduced by the presence of ketone groups to a level which is in close agreement with the yield obtained for the model ketone 12-tricosanone. This quenching of H2 production is explained by intramolecular electronic energy transfer along the chain to the carbonyl group with concomitant intermolecular charge transfer between neighboring molecules.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120711
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  • 247
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    Bulk polymerization of methyl methacrylate in the presence of poly(methyl methacrylate). II. Effect of oxygen (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2145-2147 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Tab.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120934
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  • 248
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    Effect of neighboring groups in macromolecular reactions: Distribution of units (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2165-2185 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The problem of the complete description of the sequence distribution of units in products of macromolecular reactions is discussed. The exact mathematical solution is proposed based on the muitiplet method and rate constants and including the distribution of reacted units as well as nonreacted units. Various approximate solutions of the same problem, i.e., Markovian approximations of the first, second, and third order and an approach based on the consideration of the kinetics of transformations of the sequences of reacted units (B approximation) are considered. To compare the efficiency of various methods of calculation some characteristics of the distribution of units are estimated following exact and approximate equations at various ratios of rate constants.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170121002
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  • 249
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    Interaction of organo-alkali compounds with unsaturated hydrocarbons (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2187-2197 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The stability of disodium tetramer of α-methylstyrene (“living” polymer) in THF and in a THF-α-methylstyrene mixture has been investigated by spectrophotometry. It was found that at 25°C and at concentrations lower than the equilibrium concentration α-methylstyrene greatly stabilizes the process leading to disappearance of the main absorption band (λmax = 340 mμ) of “living” polymer. In this case isomerization of “living” polymer is accompanied by quantitative conversion of the compound having λmax = 340 mμ into a new compound with λmax = 430 mμ. The constants of the disappearance rate D340 and the activation energies of the process were determined in THF and in a THF-α-methylstyrene mixture. The introduction of small amounts of α-methylstyrene into living polymer at 25°C markedly increases its activity in the course of propagation. The experimental results are considered from the standpoint of formation of complexes of living polymer with α-methylstyrene.
    Additional Material: 5 Ill.
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  • 250
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    Photostabilization of polypropylene. II. Stabilizers and hydroperoxidesFor the previous paper in this series, see Carlsson et al.1Issued as NRCC 14164. (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2217-2233 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of various polyolefin photostabilizers on the thermal and photodecomposition of model and polymeric hydroperoxides have been investigated, both in the liquid and solid phases. Several extremely effective ultraviolet stabilizers belonging to the metal chelate class can cause the rapid thermal decomposition of model and polymeric hydroperoxides. Although stabilizers did not reduce the quantum yield for polypropylene hydroperoxide photolysis, several additives can scavenge hydroxyl and macroalkoxy radical products which result from hydroperoxide photolytic cleavage. Ultraviolet stabilizers which were found to trap radicals were able to prevent the photodegradation of polypropylene which already contained a significant concentration of hydroperoxide groups. Highly effective polypropylene ultraviolet stabilizers probably operate by a range of mechanisms including hydroperoxide decomposition, radical scavenging and singlet oxygen quenching.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170121006
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  • 251
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    Metal compounds in free-radical processes. III. Polymerization of acrylonitrile initiated by copper (II) nitrate in presence or absence of triphenylphosphineFor Part II, see Horanská and Bartoň.1 (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2273-2282 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The bulk polymerization of acrylonitrile (AN) initiated by copper (II) nitrate, Cu(II), in the absence of light has been studied. The rate of the AN polymerization may be expressed in the Cu(II) concentration range from 5 × 10-4 to 1 × 10-1 mole 1.-1 by the equation, Rp = k5[Cu(II)]0.68, where k5 = KAN[AN]/(1 + KAN[AN]). From the spectrophotometric measurements the values of 0.70 l./mole and 0.08 l, mole were obtained for the equilibrium constant at 20 and 60°C, respectively, KAN = [C]/[AN]-[Cu(II)], corresponding to the formation of the complex C from acrylonitrile and copper (II) nitrate. An addition of triphenylphosphine (C6H5)3P into the polymerization system reduces Rp, and no polymerization takes place at all provided [(C6H5)3P]/[Cu-(II)] ≧ 5. The retardation effect of (C6H5)3P on the polymerization of AN initiated by Cu(II) is attributed to a competitive reaction of Cu(II) with (C6H5)3P in which Cu(II) is reduced and the product of this reduction CuNO3·2(C6H5)3P is inactive with respect to the polymerization of AN.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170121009
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  • 252
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    Polyphenylquinoxalines with high glass transition temperatures via highly fused aromatic tetraamines (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1925-1931 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of polyphenylquinoxalines has been synthesized by the reaction of p,p′-oxydibenzil with aromatic tetraamines containing varying numbers of fused rings. It was found that the glass transition temperatures of the resultant polymers increased as the the number of adjacent fused rings in the polymers was increased. This provided the basis for achieving glass transition temperatures for the polymers in excess of 400°C, substantially higher than the state-of-the art polyphenylquinoxalines. All of the polymers displayed both the good thermal stability and the solubility in m-cresol characteristic of the polyphenylquinoxaline family of polymers.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120907
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  • 253
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    Photosensitized dehydrochlorination of poly(vinyl chloride). III. Reaction of thermally degraded poly(vinyl chloride) with hydrogen chloride (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1933-1943 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Films prepared from thermally degraded poly(vinyl chloride) were photolyzed in the presence of hydrogen chloride. When the light was filtered through a Pyrex disk, the absorbance in the region between 270 nm and about 415 nm decreased and reached a minimum value but the absorbance increased at wavelengths shorter than 270 nm and longer than 415 nm. Maximum bleaching occurred at a wavelength which depended on that of the irradiating light. When the Pyrex filter was omitted, an additional slower photodehydrochlorination reaction was superimposed on the photobleaching reaction. Photolysis of hexane or ethanol solutions of 1,8-diphenyloctatetra-1,3,5,7-ene and hydrogen chloride showed a similar reaction involving bleaching of the absorption of the polyene structure. The problems of using absorbance as an indication of the extent of the photodegradation of poly(vinyl chloride) are discussed.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120908
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  • 254
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    Influence of conformational changes of co(III)-poly-N-vinyl-2-methylimidazole complexes on electron-transfer reactions of the complexes (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2207-2216 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to study the effect of conformational changes in electron-transfer reactions of Co(III)-polymer complexes, cis-[Co(III)(en)2LCl]Cl2, where the ligand L is PVI(poly-N-vinyl-2-methylimidazole) or NEI (N-ethylimidazole), was prepared. Electrontransfer reactions with ferrous sulfate or FeEDTA2- were examined mainly with respect to the effects of the degree of coordination, ionic strength, composition of reaction solvent, in relation to the conformational changes. In the reduction by FeEDTA2-, an increase in the degree of coordination of Co(III)-PVI brought about an extreme increase in its reactivity, while it was almost unity in the reduction by ferrous sulfate. With an increase in the ionic strength, the reactivity decreased due to the electrostatic shielding in the reduction by FeEDTA2-. It was noticed that the reaction of Co(III)-PVI was much more enthalpically disadvantageous due to the shrinkage of the polymer chain than that of Co(III)-NEI, when neutral salts were added. In an aqueous alcoholic solvent, an increase in the alcohol concentration accelerated the reaction with FeEDTA2-, and especially in the reaction of Co(III)-PVI, the maximum and minimum points of the reactivity were observed. On increasing the reaction temperature, the maximum and minimum points shifted to lower alcohol concentration. These phenomena are discussed in regard to the conformational changes of Co(III)-PVI.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170121005
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  • 255
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    Kinetics of free-radical copolymerization of α-methylstyrene and styrene (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2235-2254 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The free-radical copolymerization of α-methylstyrene and styrene has been studied in toluene and dimethyl phthalate solutions at 60°C. Gas chromatography was used to monitor the rate of consumption of monomers. For styrene alone, the measured rate of polymerization Rp and M̄n of the polymer coincided with values expected from previous studies by other workers. Solution viscosity η affected Rp and M̄n of styrene homopolymers and copolymers as expected on the basis of an inverse proportionality between η1/2 and termination rate. The rate of initiation by azobisisobutyronitrile appears to be independent of monomer feed composition in this system. Molecular weights of copolymers can be accounted for by considering combinative termination only. The effects of radical chain transfer are not significant.A theory is proposed in which the rate of termination of copolymer radicals is derived statistically from an ideal free-radical polymerization model. This simple theory accounts quantitatively for Rp and M̄n data reported here and for the results of other workers who have favored more complicated reaction models because of the apparent failure of simple copolymer reactivity ratios to predict polymer composition. This deficiency results from systematic losses of low molecular weight copolymer species in some analyses. Copolymer reactivity ratios derived with the assumption of a simple copolymer model and based on rates of monomer loss can be used to predict Rp values measured in other laboratories without necessity for consideration of depropagation or penultimate unit effects. The 60°C rate constants for propagation and termination in styrene homopolymerization were taken to be 176 and 2.7 × 107 mole/l.-sec, respectively. The corresponding figures for α-methylstyrene are 26 and 8.1 × 108 mole/l.-sec. These constants account for the sluggish copolymerization behavior of the latter monomer and the low molecular weights of its copolymers. The simple reaction scheme proposed here suggests that high molecular weight styrene-α-methylstyrene copolymers can be produced at reasonable rates at 60°C by emulsion polymerization. This is shown to be the case.
    Additional Material: 3 Ill.
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  • 256
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    Block polymers from isocyanate-terminated intermediates. II. Preparation of butadiene-∊-caprolactam and styrene-∊-caprolactam block polymers (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2613-2622 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polystyrene-nylon 6 and polybutadiene-nylon 6 block copolymers have been prepared from isocyanate-terminated prepolymers. From extraction and fractionation data the products obtained were found to be mixtures of both homopolymers and pure block copolymer. The polybutadiene-nylon 6 copolymers are extremely pliable at ambient temperatures even at high ∊-caprolactam contents (70-80 wt-%). This is true even though these copolymers show a crystalline melting point at 213°C similar to poly-∊-caprolactam. Presumably this unusual behavior occurs because of the nature of the synthesis which renders the butadiene portion of these copolymers the continuous phase. Plasticity measurements indicate that pliability is dependent on the molecular weight of the block poly-∊-caprolactam.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170121114
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    Synthesis and properties of phosphorus-containing polycarbonates (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2357-2367 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aromatic polycarbonates were prepared from several dichloroformates with phosphorus-containing bisphenols, such as bis(p-hydroxyphenyl)methyl phosphine oxide and bis(p-hydroxyphenyl)phenyl phosphine oxide, or with nonphosphorus bisphenols by interfacial, low-temperature solution, and high-temperature solution polycondensation. The interfacial polycondensation gave the best results for polycarbonates, from which colorless, transparent, and fairly though films were cast. In contrast to analogous nonphosphorus polycarbonates, the phosphorus-containing polycarbonates exhibited lower polymer melt temperatures, greater range of solubility, and better self-extinguishing properties, but less stability to alkali and acid. Thermal degradation of the typical phosphorus polycarbonates proceeded in two steps, and the activation energies for the maximum rates of weight loss range from 29 to 45 kcal/mole.
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    URL: http://dx.doi.org/10.1002/pol.1974.170121017
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    Stereoregularity and polymerization mechanism of polymethacrylonitriles determined by 13C-NMR spectroscopyPresented at the 29th Autumn Meeting, The Chemical Society, Japan, Hiroshima, Oct. 10-13, 1973. (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2377-2384 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Carbon-13 nuclear magnetic resonance (13C-NMR) spectra of polymethacrylonitriles prepared under various conditions were measured. In acetone solution, the α-methyl carbon absorptions were split into triads and partially into pentads, and the methylene carbon absorptions into tetrads. In trifluoroacetic acid solution, the α-methyl carbon absorptions were split into pentads and the cyano carbon absorptions into triads. The triad, tetrad, and pentad tacticities determined from 13C-NMR spectra were compared with dyad tacticities determined from proton NMR spectra. The stereoregularity of the polymers which are γ-ray-initiated in liquid phase at temperatures near melting point (-35.8°C) and in the solid state differs from that of the polymers radically initiated at -20 to 80°C. The stereoregularity and the conversion suggest the existence of an ionic mechanism in the polymerization at low temperatures.
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    URL: http://dx.doi.org/10.1002/pol.1974.170121019
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    Copolymerization of styrene. V. Copolymerization with α-cyanocinnamamide (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2435-2447 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copolymers of styrene with α-cyanocinnamamide were prepared by free radical initiation in bulk and in DMF solution and also by thermal initiation in bulk. The copolymerization parameters were determined by the conventional scheme of copolymerization and by an improved scheme taking into account the penultimate unit. Different values of the copolymerization parameters were obtained at the above mentioned different polymerization conditions, indicating the existence of a solvent effect. The influence of the comonomer on some of the basic properties, like intrinsic viscosity, solubility, melting range, and glass transition temperature and on some mechanical and behavior properties of the copolymers was studied in comparison with homopolystyrene.
    Additional Material: 11 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170121024
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    Radiation-induced emulsion polymerization of ethylene. VI. Continuous flow system (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2403-2417 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radiation-induced emulsion polymerization of ethylene in a continuous flow system was carried out at 100°C by using FC-143 and potassium myristate. The polymer concentration in the latex during the course of the polymerization oscillated several times and then approached a steady-state value in a few hours in the case of short residence time. The rate of polymerization was almost constant within the residence time range of 0.2-0.9 hr. This is explained by the kinetics assuming the same mechanism previously proposed in the batch system, that is, the number of polymer particles in this range is considered to be constant. Gel formation was observed at longer reaction times in spite of the continuous supply of myristate micelles, possibly because large polymer particles are produced in this stage. The concentration of carbonyl group in the polymer produced by chain transfer to absorbed myristate ion changes in the same way as the polymer concentration with reaction time. The methyl group in the polymer is produced mainly by chain transfer to the polymer, and the concentration is nearly constant during the polymerization except in the initial stage. The rate constants for the continuous polymerization were very different from the batch polymerization previously studied, despite their similarities in nature. The mass transfer rate of the emulsifier from the micelles to the polymer particles requires future study.
    Additional Material: 16 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170121022
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  • 261
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    Mechanism of charge-transfer polymerization. XI. Radical copolymerization of N-vinylindole with electron-accepting monomersFor Part X of this series, see Shirota et al.1 (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2199-2206 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-Vinylindole (NVI) was copolymerized with such electron-accepting monomers as fumaronitrile (FN) or diethyl fumarate (DEF) under initiation with a radical catalyst. The compositions of the copolymers varied from 1:1.1 to 1:1.85 (NVI:FN or DEF). The FN or DEF content in the copolymer increased with increase in the molar fraction of the FN or DEF monomer in the monomer feed. It was suggested that both copolymers have a 1:1 recurring unit of NVI and the electron-accepting monomer, thus being alternating copolymers, and that further addition of the electron-accepting monomer to the indole ring occurred at its electron-rich β-carbon atom.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170121004
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    Radiation-induced crosslinking and cyclization in 1,2-polybutadiene (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2255-2271 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to get information on the radiolytic changes in 1,2-polybutadiene (1,2-PB) the sol and gel fractions, the conversion of double bonds, the structure and concentration of radicals, the formation of dienes and the formation of gaseous products were measured. In addition, the dose rate dependence and temperature dependence for the conversion of double bonds were determined. G values for double bond conversion depend on molecular weight and range from 20 to 200. G values for crosslinking are about 10. A mechanism for the double bond conversion is proposed which involves initiation by a transformation of the primary radical ion in the vinyl group into a carbonium ion and a radical. This is supported by ESR measurement. Reaction of the carbonium ion with a vinyl group in the same chain gives rise to cyclization, whereas reaction with a vinyl group in a neighboring chain results in crosslinking. A comparison of the G values for conversion of double bonds with the G values for crosslinking shows that the formation of cyclic rings exceeds the formation of crosslinks by a factor of about 10. The corresponding values in 1,4-cis- and 1,4-trans-polybutadiene are much smaller [G(cl) ≃ 2; G(db) ≃ 7]. The pendent vinyl groups in 1,2-polybutadiene therefore are more reactive than the vinylidene groups in 1,4-polybutadienes.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121008
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    Reactions of models of the growth center during anionic polymerization of methacrylate esters (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2295-2304 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of α-lithioisobutyric acid esters were studied as models of partial reaction taking place during anionic polymerization of methacrylate esters. The rates of selfcondensation reactions and condensations with nonmetalated esters were determined for these models. In both cases ketoesters were the final products. Besides esters of α,α,α′-trimethylglutaric acid expected according to Michael's reaction scheme the addition of methacrylate esters to α-lithio esters also yielded oligomeric compounds due to repeated addition of methacrylate esters. The α-lithio oligomers of methacrylate esters underwent cyclization condensation which gave rise to esters of substituted cyclohexanonedicarboxylic acids. The alkali metal alkoxides slowed down all the condensation reactions of α-lithio esters investigated here. Such effect of alkoxides also appeared in the cyclization condensation of compounds formed by repeated addition of methacrylate esters, because in the presence of alkoxides the reaction mixture contained a higher amount of higher molecular weight compounds than in a system without alkoxide. The effect of alkoxides observed here is in accordance with the view that the cyclization condensation is one of the termination reactions of the anionic polymerization of methacrylate esters.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121011
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  • 264
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    Photopolymerizations initiated by oxime derivatives (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2553-2566 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A number of ester, urethane, and carbonate derivatives of biacetyl monooxime, dimethylglyoxime, and ketone oxime, were synthesized and their photolyses studied by means of ultraviolet spectroscopy. Most of the oxime derivatives photolyzed easily upon UV irradiation. Among them, however, only the free radicals formed by photolysis from the ester and carbonate of biacetyl monooxime could effectively initiate the polymerization of a vinyl monomer such as methyl methacrylate. Based on the results obtained from the monomeric reactions, syntheses of grafting polymers were made. Graft polymers were obtained by using a copolymer of methyl methacrylate and methacrylic acid-biacetyl monooxime ester (copolymer I) and that of methyl methacrylate and vinyl benzioc acid-biacetyl monooxime ester (copolymer II) in good yield and without the formation of homopolymer. It was also found that when copolymer I was employed as a grafting polymer, a considerable amount of main-chain scission was seen, but no chain degradation was noted in the case of copolymer II. Photocrosslinking was attempted by using these copolymers in the presence of divinyl benzene. It was confirmed that copolymer II was photocrosslinkable, whereas copolymer I underwent photodegradation.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121109
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  • 265
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    Further studies on the ultraviolet graft copolymerization of maleimide by vapor-phase method (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2603-2612 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Graft copolymerization of maleimide onto polyethylene and ethyl cellulose films by using its sublimation vapor was carried out under ultraviolet irradiation in the presence or absence of air; the effect of air or additives on the grafting reaction and on the nature of the grafted films was investigated. The extent of grafting gradually approached a fixed value, in spite of the continuous ultraviolet irradiation. Air retarded the grafting reaction but did not suppress the reaction nor alter the final extent of grafting. Benzoquinone showed no inhibiting effect on the grafting. The grafted polymaleimide was found to be amorphous, even though ultraviolet irradiation produces a highly crystalline homopolymer in the solid phase as well as in the liquid phase. The results were discussed in comparison with those of the vapor-phase grafting under γ-ray irradiation; the reaction is attributed to the vapor-crystal equilibrium of monomer and to the formation of short-chain crosslinks.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121113
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  • 266
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    Influence of the low molecular weight amides on the dynamic behavior of polymers (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2639-2645 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dependence of the dynamic shear modulus G′ and mechanical damping tan δ was measured for mixtures of low molecular amides with VC/VAc copolymer and polystyrene, respectively. A new secondary relaxation was found, which in some cases depends on content of moisture. The effect of molecular structure and concentration of amide is shown.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121117
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  • 267
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    Effect of nonelectrostatic interactions on the macromolecular behavior of polyelectrolytes. I. Potentiometric titrations of PLL in water and aqueous-organic mixtures (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2659-2670 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The potentiometric and viscosity behavior of salt-free solutions of the polycondensate between L-lysine and 1,3-benzenedisulfonyl chloride (PLL) and related polyelectrolytes, have been investigated in water and in aqueous-organic mixtures (acetone-water). The effects of counterions and solvent on the pH-induced conformational transition is related to hydrophobic interactions. The transition from a compact state to a more extended one shifts towards high values of neutralization with increasing length of N-tetraalkylammonium counterions. Moreover, the above transition gradually disappears as the percentage of acetone in the mixture is increased, which is interpreted as reflecting the breakdown of the compact structure due to hydrophobic interactions stabilized by bulky counterions. A linear decrease in the free energy variation ΔGt° is observed with increasing percentage of acetone up to about 40% of acetone, and a value of 1200 cal/unit is obtained for PLL in water, which is a reasonable value compared to other data for hydrophobic polyelectrolytes.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170121120
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  • 268
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    Solid-state polymerization of a cyclic diacetylene (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2467-2475 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Large polymeric single crystals of a unique ring-bridged polymer have been produced by the solid-state polymerization of a cyclic diacetylene (o,o′-diacetylenyldiphenyl glutarate). These crystals are of high thermal stability, metallic in appearance with an asbestos-like texture, infusible, and insoluble. Single-crystal x-ray diffraction investigation indicates that the polymer is monoclinic (probable space group C2/c or Cc) with a unit cell containing four monomer units of dimensions α = 20.8 Å, b = 8.0 Å, c = 9.7 Å, and β = 106°. Infrared spectra eliminate the previously suggested possibility that the solid-state reactivity of the above monomer corresponds to either reaction of the carbonyl function with the acetylenic bond or the cleavage of the ester linkage. Diffraction, dichroism, and Raman spectral studies indicate instead that the reaction proceeds by 1,4-addition polymerization at the diacetylene group to produce a trans-trans polymer of structure where the curved lines represent the di-(o-phenyl)-glutarate linkages which are on opposite sides of the chain for adjacent monomer units.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170121102
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  • 269
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    Modification of PVC. XXVI. Syntheses and photocrosslinking of polysulfide pendant poly(vinyl chloride) (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2497-2509 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(vinyl chloride) pendant with polysulfide (PS-PVC) having various degrees of substitution, various S substituents, and various numbers of atoms in the sulfur chain has been synthesized by the reaction of poly(vinyl chloride) with a thiol, sulfur, and triethylamine in dimethylformamide at 30°C for 0.4-5 hr. The photocrosslinking reaction has been investigated under ultraviolet irradiation at 250-450 mμ. The photocrosslinking reaction of PS-PVC is influenced by the degree of substitution, the nature of the S substituent, and the number of atoms in the sulfur chain. The degree of photocrosslinking r increased in the order, n-C4H9— 〈 n-C8H17— 〈 C6H5CH2— 〈 i-C3H7— 〈 t-C4H9—. On the photocrosslinking of PS-PVC having two different S substituents, r increases in the similar order for aliphatic substituents and in the order NO2C6H4— 〈 ClC6H4— 〈 C6H5CH2— 〈 CH3C6H4— 〈 t-C4H9C6H4— 〈 C6H5— for the aromatic substituents. Further, r increases markedly with the increase of sulfur chain number for all PS-PVC. The chemical structure of the crosslinks and the crosslinking mechanism are discussed on the basis of the results.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170121104
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    Relationship between radical polymerization rate and initiator concentration in various solvents (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2581-2593 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methyl methacrylate and styrene were polymerized by using 2,2′-azobis(2,4-dimethyl valeronitrile) as initiator in various solvents. When a poor solvent is used, the dependence of polymerization rate Rp on initiator concentration [C] is small and can be treated by equations for the analysis of the polymerization with primary radical termination. With a good solvent, the dependence of Rp on [C] is so large that such equations are not applicable. Thus, the [C] dependence in a good solvent is explained qualitatively through the molecular weight dependence of rate for termination between polymer radicals, based on the excluded volume effect.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170121111
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    Low-angle x-ray estimation of macromolecular parameters of the scattering particles in Agave sisalana (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2595-2602 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Various macromolecular parameters of Agave sisalana (sisal) fiber were investigated by the low-angle x-ray scattering method. The well known Kratky camera of the latest design was utilized for the experimental measurements. The sample studied was a densely packed colloidal system belonging to a general micelle system, and the theories of Kratky and Kratky and Porod were utilized to estimate the parameters. Pore analysis of the substance yields a value for the specific inner surface of the dispersed phase of 0.406 × 10-1 m2/cm3; the transversal length is the same as the length of inhomogeneity, 107.31 Å, and the length of coherence is 342.21 Å. The air fraction of the scattering particles was found to be 0.01%.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170121112
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    Swelling measurement of some ethylene copolymers crosslinked by dicumyl peroxide (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2631-2638 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Swelling equilibrium of crosslinked ethylene copolymers prepared by the curing of ethylene-vinyl acetate (EVA), ethylene-ethyl acrylate (EEA), and ethylene-acrylic acid (EAA) with dicumyl peroxide (DCP), has been measured in toluene at 23°C. The stress-strain behavior of the swollen EVA and EEA networks was in accord with that predicted from the statistical rubber elasticity theory, while that of the swollen EAA network was divergent. The concentration dependence of the polymer-solvent interaction parameter for the EAA network-toluene system was observed to be highest, while that for the EVA network-toluene system remained nearly zero. The order of the reactivity of pendant groups in the copolymers by radicals from DCP was estimated to be carboxyl 〉 acetyloxy 〉 ethoxycarbonyl group.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170121116
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    Conductivity of carbon black-loaded styrene-butadiene rubber (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2651-2657 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Styrene-butadiene rubber (SBR) charged with 50 phr of HAF carbon black has been found to show a positive temperature coefficient of resistivity close to 0.07/°C at 27°C. Beyond a point (75°C) of minimum conductivity, however, it behaves as a normal noncrystalline semiconductor with a resistivity which decreases with rise of temperature with an activation energy of 0.56 eV. Blending the composition with poly(vinyl chloride) (PVC) shifts the minimum towards lower temperatures. The descending branch of the conductivity versus reciprocal absolute temperature characteristic is probably associated with thermal expansion of tunnelling paths separating the conducting carbon particles.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170121119
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  • 274
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    Photoreactions of N-vinylcarbazole induced by metal salts. II. Further studies on the photocationic polymerization sensitized by sodium chloroaurate(III) in nitrobenzenePart I: Tazuke, Asai, and Okamura.2 (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 45-56 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Further investigations of the photopolymerization of N-vinylcarbazole(VCZ) sensitized by sodium chloroaurate(III) in nitrobenzene were undertaken under irradiation of near-ultraviolet light at 30°C. Copolymerization with isobutyl vinyl ether and the kinetic behavior of polymerization were studied. These propagation and chain-breaking features were discussed in comparison with those obtained in the thermal polymerization. Electron spin resonance spectroscopy was conducted at 77°K in various systems.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120105
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    Copolymers of conjugated dienes with maleic acid monoesters. IV. Reactivity ratios in copolymerization of isoprene with maleic acid monoesters (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 231-240 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Research was carried out on copolymerization of isoprene with maleic acid monoesters in the presence of free radicals (AIBN). The aim of the study was to observe the effect of the different monoesters obtained with normal alcohols of the aliphatic series: monoethyl maleate, monopropyl maleate, monobutyl maleate, monoheptyl maleate, monolauryl maleate, and monocetyl maleate. On the basis of reactivity ratios determined by the Fineman-Ross method and compared with the Mayo-Lewis method, all the systems studied are typical cases of heterocopolymerization. The parameter r1 is constant for this homologous series with the exception of the low terms. The experimental results agree with the ultimate model equation (with deviation at very high values of [M10]/[M20]), but not with the copolymer composition equation which considers the effect of the penultimate unity (penultimate model). Characterization of the sequential distribution is also presented (considering the effect of the terminal group only), and deviations of the experimental results are also discussed.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120121
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    Studies on the photooxidation mechanism of polymers. I. Photolysis and photooxidation of polystyrenePresented in part at IUPAC Symposium on Photochemical Process in Polymer Chemistry, June 12-15, 1972, Louven, Belgium. (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 273-294 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new mechanism has been proposed for the photooxidation of polystyrene as film and in benzene. The initial stage of the photooxidative degradation may involve reactions of singlet oxygen with polystyrene molecules. Singlet oxygen may be formed in the reaction between excited benzene ring in polystyrene molecule and molecular oxygen. The addition of singlet oxygen quenchers such as 1,3-cyclohexadiene or β-carotene reduces the rate of polymer degradation in benzene solution. The mechanisms of the photolysis of polystyrene as film and in benzene solution, in vacuo and in the presence of oxygen, are discussed and interpretations proposed. The pronounced yellowing of polystyrene during the photooxidation process is interpreted as a reaction involving benzene ring-opening photooxidation in polystyrene molecule. These results were obtained by comparing ultraviolet and infrared spectra in experiments of photooxidation of pure liquid benzene and polystyrene film.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120203
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    Formation and flocculation of graft copolymer micelles (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 323-335 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Criteria for formation and flocculation of micelles from pure graft copolymers were investigated in single selective solvents by turbidimetry with the use of two series of graft copolymers from poly(vinyl acetate) (PVAC), i.e., PVAC-styrene graft copolymers with one branch and PVAC-methyl methacrylate graft copolymers with one and several branches. These graft copolymers could be completely coagulated through two processes in the selective solvents which had widely different ⊖ temperatures. The first process is the formation of micelles. One sequence, i.e., either backbone or branch of the graft copolymers, becomes desolvated under conditions similar to those for the corresponding homopolymer. This results in formation of the core of the micelle, the other soluble sequence extending from the surface of the core into the solvent phase. As the soluble chains cover the micelle core, no macroscopic phase separation occurs, but a stable dispersion is formed. The second process is that the micelle becomes too unstable to exist as dispersed when the solvency of the medium for the soluble sequence decreases to a certain degree. As a result, flocculation of the micelle finally takes place.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120206
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    Effect of chain interpenetration on polymer-polymer interaction in solution (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 337-345 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two series of monodisperse polystyrenes have been prepared with a molecular weight range of 3,000 to 300,000. One series was lightly substituted with dimethylbenzylamine groups, the other with 2,6 dinitro-4-benzoyloxyphenol groups. Members of each series were dissolved together in benzene solution in the range of 0.1-30%, and the equilibrium constant for the formation of the ammonium phenolate ion pair measured. Also measured was the corresponding equilibrium constant between comparable small molecular weight analogs, and between these analogs and the substituted polymers. The degree of association found between the models and between the models and the polymers was independent of molecular weight, but deviations were found in the polymer-polymer interaction. Normal equilibrium constants were found at high polymer concentrations indicating that chain interpenetration occurred freely. At low concentrations of polymer, if several links per chain were possible it was found an excess of linkages were formed. If only one link per chain was possible, low degrees of association were found for high molecular weight polymers, but the effect was not as large as a consideration of excluded volumes on a spherical model would predict.
    Additional Material: 6 Tab.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120207
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    Photopolymerization of methyl methacrylate with the use of iodine as the photoinitiator (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 375-386 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetics of photopolymerization of MMA at 40°C with the use of iodine as the photoinitiator was studied. At low range of iodine concentration (〈 0.0004M), the rate of polymerization was proportional to square root of iodine concentration and the monomer exponent was 2.5, while at a higher range of iodine concentration, (0.0005-0.002M) the initiator exponent and monomer exponent were zero and 3.6-3.8 (i.e., close to 4), respectively. The chain-transfer constant of iodine at 40°C was found to be 6.0. Polymerization was found to be largely inhibited in the presence of relatively high concentrations of iodine (〉 0.005M) and also in presence of hydroquinone. Kinetic and other data indicate a radical mechanism of polymerization involving complexation of monomer molecules with iodine prior to radical generation, and termination is believed to take place bimolecularly at low iodine concentrations and unimolecularly, involving reaction with iodine, at high iodine concentrations (initiator termination).
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120210
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    Synthesis of polymers by using divalent metal salts of mono(hydroxyethyl) phthalate: Metal-containing polyurethanes (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 455-468 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: As difunctional compounds containing an ionic bond in the molecule, divalent metal salts (I) of mono(hydroxyethyl) phthalate were prepared in high purity and high yield. Mg and Ca were selected as divalent metal. Metal-containing polyurethanes containing ionic links in the main chain were synthesized by the polyaddition reaction of I or, I-glycols with diisocyanates. The polyurethane obtained were glassy materials or white powders, depending on the species of diisocyanates and glycols. Close agreement between observed and calculated values of metal content of the polyurethanes were obtained. The viscosities (in dimethyl-formamide) of the polyurethanes decreased markedly with increasing of metal content. Moreover, the decomposition temperatures were lowered by introduction of metals into the polyurethanes. However, the decomposition rates of metal-containing polyurethanes were lower than those of polyurethanes not containing metal.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120216
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    Activation energy and entropy change for tactic placements in PVC (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 483-486 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120218
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    Modification and characterization of polystyrene surfaces used for cell culturePaper presented in part before the Biomedical Applications of Polymers Symposium, American Chemical Society National Meeting, Chicago, Aug. 26-31, 1973. (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 489-497 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Surfaces of polystyrene Petri dishes used for cell culture were chemically modified by 5% fuming sulfuric acid. The sulfonation was performed at room temperature for various times. Formation of polar groups takes place essentially on the surface of the polymer. Wettability and ionic character of the modified surfaces were determined by contact angle measurements and surface conductivity measurements, respectively. Radioactive calcium (45Ca) adsorption at these surfaces was investigated by means of radiotracer techniques. The chemical composition (concentration of polar sites produced) of these modified polystyrene surfaces was thus determined. It was found that the wettability of these surfaces is directly related to the concentration of sulfonate groups. The cation-exchange capacity of treated surfaces with inorganic cations (Na+, Mg2+, Ca2+, and Al3+) were determined by the radiotracer technique.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120301
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  • 283
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    Poly-1-acryloylbenzotriazole as polyester and polyacrylamide precursor (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 553-559 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1-Acryloylbenzotriazole was prepared and polymerized. The resulting poly-1-acryloylbenzotriazole gave pure polyacrylic esters and polyacrylamides by reaction under mild conditions with alcohols and amines.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120306
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  • 284
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    Processability characteristics of chlorinated poly(vinyl chloride) (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 255-264 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chlorinated poly(vinyl chloride) (CPVC) is known to have a higher softening temperature than conventional poly(vinyl chloride) (PVC). Its processability characteristics are, however, different; it has been reported that CPVC is more difficult to process. However, only limited information on the processability characteristics is available. This paper describes some studies of the flow behavior of CPVC melts in a capillary rheometer. The true melt viscosity and activation energy were determined between 190° and 210°C for a number of samples, and they appear to be related to the cohesive energy density of the samples. It was observed that melt fracture, i.e., gross distortion of the extrudate, occurs even at low shear rates in samples having a high chlorine content. This has been attributed to the relatively high pressures that have to be used, the pronounced non-Newtonian nature of the melt, and melt elasticity. It is postulated that melt elasticity could result from crosslinking at the site of the double bond which is known to be formed by dehydrochlorination.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120201
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  • 285
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    Gel-permeation chromatography. IX. Instrumental design and computer interfacing of a GPC molecular weight detector system (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 307-322 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The detailed design and computer interfacing of a GPC molecular weight detector based on a real time viscometer are described. The working drawings presented will permit one to fabricate and duplicate the viscometer and the complete GPC molecular weight detector system. The uses and advantages of a laboratory automation system in analyzing GPC results are also described.
    Additional Material: 17 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120205
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  • 286
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    Aromatic polyethers, polysulfones, and polyketones as laminating resins. II (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 651-662 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,3-Bis(p-phenoxybenzenesulfonyl)benzene and 4,4′-bis(p-phenoxybenzenesulfonyl)-diphenyl ether were polymerized with isophthaloyl and terephthaloyl chloride in Friedel-Crafts type polymerizations. These polymers had 5-cyanoisophthaloyl units in the backbone, obtained by using 5-cyanoisophthaloyl chloride as part of the acid chloride monomer. A number of catalysts were screened to effect the trimerization of the pendant nitrile groups in the polymer to the triazines. Model reactions were carried out for each polymer. Physical and thermal properties of the laminates obtained from these polymers are discussed.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120315
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  • 287
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    Epoxy/modifier block copolymers (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 689-705 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The curing of epoxy resins with anhydrides in the presence of dihydroxyl-terminated polyester or polyether modifiers produces block copolymer structures in which one “block” is the crosslinked epoxy/anhydride network and the other block is the linear modifier segment. The morphology of the cured system is dependent upon modifier molecular weight. The critical molecular weight of polycaprolactone and poly(propylene oxide) is 3000-5000. Below this level, single morphological phase systems are obtained, but two-microphase systems result above this level. This behavior is displayed by several epoxy resins. Two-phase systems display a superior balance of heat distortion temperature and impact strength, thus providing tough systems with greater elevated temperature capabilities than are obtained with single-phase systems.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120318
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  • 288
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    Synthesis of polyamides from pseudo dibenzoylphthaloyl chlorides and aliphatic diamines (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 719-727 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New pseudo dibenzoylphthaloyl chlorides, namely, 2,5-dibenzoylterephthaloyl, 4,6-dibenzoylisophthaloyl, and 4,6-di(p-toluyl)isophthaloyl chlorides, were synthesized as monomers. The ring-opening polyaddition reaction of the pseudo dibenzoylphthaloyl chlorides with aliphatic diamines in N-methyl-2-pyrrolidone afforded a new class of polyamides having inherent viscosities of 0.2 ∼ 0.6 in quantitative yield. The solution polymerization was almost completed within 30 min at room temperature. All of the polyamides were soluble in a wide range of solvents including tetrahydrofuran. These polymers began to decompose at around 300°C both in air and under nitrogen as determined by differential thermal analysis (DTA) and thermogravimetric analysis (TGA).
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120402
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  • 289
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    Photoinduced polymerization of maleic anhydride in dioxane (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 785-792 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Maleic anhydride (MAn) was irradiated with ultraviolet light in dioxane at 35°C without initiator, and predominantly a MAn oligomer was obtained with a small quantity of cyclic dimer of MAn. Mass spectrometric, NMR, and elementary analysis investigation of the oligomer showed that it is composed of about four MAn units and one dioxane molecule per molecule.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120408
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  • 290
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    Synthesis of zirconium poly-O-amidoximesPresented in part at the 166th American Chemical Society Meeting, Chicago, 1973 (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 799-805 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of zirconium poly-O-amidoximes was affected by using both interfacial and aqueous solution techniques. Reaction is rapid. The yield for the synthesis of analogous titanium product is Cp2ZrCl2 〉 Cp2TiCl2 which is consistent with that predicted by the hard-soft acid-base theory.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120410
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  • 291
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    Polymerization and reaction rate studies on substituted phenylmethylbis(dimethylamino)silanes (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 825-836 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of seven para- or meta-substituted phenylmethylbis(dimethylamino)-silane monomers has been carried out. These silanes were polymerized with 1,4-bis(hydroxydimethylsilyl)benzene in tetrahydrofuran at 30°C, and the polymerization kinetics were followed by monitoring dimethylamine evolution for 200 min. The polymers were quenched by precipitation in methanol and molecular weight data were obtained. The polymerizations followed second-order kinetics in every case as evidenced by the linear plots of 1/(a - x) versus time. The molecular weight data generally correlated with the specific reaction rate constant k2 to show an increasing polymer molecular weight with increasing polymerization rate, although the range of k2 values obtained for the substituted aminosilanes was relatively small (2.50 × 10-5-6.67 × 10-5 l./mole-sec). The value of k2 increased in the following order: p-OCH3, p-F, m-CH3, H, m-OCH3, p-CF3, 3,5-di(CF3). The logarithms of the rate constants correlated with the σ constants for the substituents, with a reaction constant, ρ of 0.391. The displacement at silicon in these reactions is discussed in terms of bimolecular mechanisms in which a four-center transition state may participate.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120413
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  • 292
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    Synthesis and characterization of isomeric polyesters based on sebacic acid and hexanediols (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 865-874 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Isomeric homopolymers and random copolyesters based on sebacic acid and isomeric hexanediols were synthesized by condensation techniques and characterized by NMR, GPC, intrinsic viscosity, and DSC. Among the homopolymers, only the polyester derived from the linear 1,6-hexanediol was found to be crystalline. Typical melting points were 65-70°C, depending on molecular weight, and a Tg of -62°C was measured on a high molecular weight sample. Other isomeric homopolymers derived from the branched diols 2-methyl-2-ethyl-1,3-propanediol and 2,5-hexanediol were amorphous tacky fluids with glass temperatures of -69 and -66°C, respectively. In the case of the random copolymers, NMR analysis was particularly useful in determining the copolymer composition or the diol isomer ratio. DSC data indicated that all the random copolymers containing the linear 1,6-diol were crystallizable and their melting points depended on copolymer composition. The heat of fusion per repeat unit of poly(hexamethylene sebacate) was found to be 32 cal/g from measurements of the molecular weight dependence of the melting point.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120416
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  • 293
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    Olefin polymers derived from Diels-Alder adducts of 1,7-octadiene and hexachlorocyclopentadiene (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 921-924 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120421
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  • 294
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    Proposed method for determining the sequence distributions of the configurations in high 1,4-polybutadienes by infrared spectroscopy (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 925-928 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120422
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  • 295
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    Copolymerization of acrylonitrile. III. Copolymerization with α-cyanocinnamamide (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 945-951 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acrylonitrile was copolymerized in solution with α-cyanocinnamamide up to low conversions. The conventional scheme of copolymerization fitted this copolymer. The basic properties, such as solubility, viscosity, and thermal behavior, of the copolymer prepared in bulk and in solution were determined.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120503
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  • 296
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    Radiation-induced emulsion polymerization of ethylene. V. Copolymerization of ethylene with hexafluoropropylene (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 627-637 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The emulsion copolymerization of ethylene with hexafluoropropylene was studied by using 60Co γ-radiation as the initiator. The apparent rate of copolymerization is proportional to the 1.6 power of ethylene fugacity. The activation volume was calculated from the pressure dependence of the apparent rate constant of copolymerization and was -30 ml/mole, which is smaller than the value reported by Wada et al. for ethylene polymerization in tert-butyl alcohol. The copolymer produced had a broad composition from ethylene-rich to alternative. As expected, the former was a crystalline, polyethylenelike copolymer, but the latter was an amorphous and rubberlike copolymer. The glass transition temperature of the copolymers increased with an increase in hexafluoropropylene content. The thermal degradation temperature in an atmosphere of nitrogen decreased slightly with introduction of hexafluoropropylene in polyethylene, but the thermal degradation behavior in air was complicated by the introduction of hexafluoropropylene.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120313
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  • 297
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    Thermoxidative degradation leading to gel in poly(ethylene terephthalate) (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 709-717 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(ethylene terephthalate) oxidizes on heating at 300°C in an air stream. Various literature has cited crosslinking under such conditions through a butanetriol or a biphenyltricarboxylic acid. In this study gelled polymer was found to contain the latter trifunctional compound, but not the former. In addition, 4,4′-biphenyldicarboxylic acid was found in the degraded gel. There is further indication for the presence of other multifunctional species. All components are consistent with general free-radical arylation mechanisms.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120401
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  • 298
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    Copolymerization of carbon dioxide and N-phenylethylenimine (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 729-736 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copolymerizations of carbon dioxide and N-phenylethylenimine were carried out with the use of various catalysts and solvents. The infrared spectrum of the polymer produced showed the characteristic absorption peak at 1730-1735 cm-1 based on the urethane linkage.The content of the urethane linkage decreased in the following order: Mn(acac)2 ≈ MnCl24H2O 〉 Al(OBu)3 〉 Ti(OBu)4 〉 ZnCl2 ≫ BF3OEt2 = VCl3 = Mn(acac)3 = FeCl3 = CrCl3 · 6H2O = 0. The manganase (bivalent) catalyst in combination with n-hexane solvent was found to be the best system for the copolymerization, and this system received detailed study. Generally speaking, both the polymer yield and the content of the urethane linkage increased with increasing content of carbon dioxide in the feed as well as with increasing polymerization temperature. From the fractionation of polymer in methanol, it was found that the produced polymer is composed of both homopolymer of N-phenylethylenimine and copolymer of N-phenylethylenimine and carbon dioxide. The content of the urethane linkage of the copolymer thus fractionated was as high as about 80%.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120403
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  • 299
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    Near-infrared spectrum of cellulose: A new method for obtaining crystallinity ratios (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1143-1150 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absorption bands in the near-infrared (NIR) spectrum of cellulose were correlated with crystalline and noncrystalline regions and used to derive a new crystallinity ratio. NIR crystallinity ratios of both natural and regenerated celluloses were measured and compared with x-ray diffraction values. The data indicates that the NIR crystallinity ratio may also depend upon crystallite size.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120601
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  • 300
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    Cationic polymerization of styrene by acetyl perchlorate: Molecular weight distribution of polystyrene and nature of the propagating species (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 967-984 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To clarify the nature of the propagating species in cationic polymerization of styrene catalyzed by acetyl perchlorate, the molecular weight distribution of the polymer was investigated under various conditions. The molecular weight distribution curve for the polymer obtained in methylene chloride at 0°C showed a double peak phenomenon. This suggests that two or more kinds of propagating species participate simultaneously in the propagation reaction. The weight fraction W(H) of the polymer corresponding to the higher molecular weight peak increased with increasing polarity of the solvent. W(H) decreased when the concentration of the ionic species was increased either by an increase of the catalyst concentration or by the addition of the common salt such as tetra-n-butylammonium perchlorate. On the other hand, the position of the peak in the molecular weight distribution curve was independent of polymerization conditions. It was concluded that the higher molecular weight part of the polymer was produced under conditions for conductive to dissociation of the propagating species and the less dissociated propagating species was responsible for the lower molecular weight part of the polymer.
    Additional Material: 16 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120505
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