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  • Physics  (487)
  • 1980-1984
  • 1975-1979  (487)
  • 1950-1954
  • 1977  (487)
  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1-4 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The melting behavior of diamides of general formula (n-CpH2p+1)CONH(CH2)qNHCO(nCpH2p+1) has been investigated by differential scanning calorimetry (DSC). The close similarity of the melting behavior of these low molar mass compounds with that of polymeric amides is discussed in terms of restricted conformational disorder in the amorphous state, due to the high degree of retention of hydrogen bonding.
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  • 2
    Electronic Resource
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 5-13 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of a series of polyamides and copolyamides containing α-truxillic and adipic units in the chain is reported. The thermal degradation of these polymers was investigated by direct pyrolysis in the ion source of a mass spectrometer. Thermal degradation reactions were followed directly by this method by detecting the thermal- and electron-impact-induced fragments. The results obtained show a good correlation between the intensity of mass peaks characteristic of truxillic and adipic moieties and the composition of the copolyamides, as ascertained by elemental analysis. This is an important result since it shows the potential of the direct pyrolysis method in the analysis of copolymers. Relevant information on the relative thermal stabilities of the polymers investigated has been also obtained.
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  • 3
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 15-30 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Shake-up phenomena in a series of para-substituted polystyrenes have been studied by ESCA. Comparison with other spectroscopic data and with theoretical calculations within the sudden approximation, equivalent cores model, and CNDO SCF MO formalism identifies the shake-up structures as arising predominantly from π*← π transitions involving the highest occupied and lowest unoccupied orbitals of the pendant phenyl groups.
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  • 4
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 31-38 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The extent of binding of methyl orange, ethyl orange, propyl orange, and butyl orange by poly(vinylpyrrolidone) has been measured in aqueous solutions of inorganic electrolytes such as NaCl, LiCl, NaSCN, and NaClO4 by an equilibrium dialysis method. The effect of the salts on the first binding constants and the thermodynamic functions which are accompanied by the dye - polymer association process was investigated relative to the corresponding values in the absence of such salts. It was found that in aqueous solutions of NaCl and LiCl the enthalpy change accompanying the binding is small and the largest contribution to the free energy of binding is from the positive entropy gain. For NaSCN and NaClO4, the values of ΔF° and ΔH° were both large and negative and the value of ΔS° was small and negative. Thus, the favorable free energy for the complex formation was due entirely to the negative enthalpy term. These characteristics of the thermodynamic quantities are discussed in terms of changes in structural properties of water in the vicinity of the binding entities and conformational changes of the polymer to which the dye is bound due to the added foreign electrolytes.
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  • 5
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 51-63 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactivity ratios for acrylonitrile - vinyl chloroacetate systems have been determined for radical copolymerization at 60°C in dimethylformamide. The values of the ratios calculated by the linear graphical method of Kelen and Tüdös were as follows: r1 = 4.05 ± 0.1 and r2 = 0.001 ± 0.001 for acrylonitrile (AN) - vinyl monochloroacetate (VCAc), r1 = 7.0 ± 0.25 and r2 = 0.05 ± 0.015 for acrylonitrile - vinyl dichloroacetate (VDAc), r1 = 7.13 ± 0.25 and r2 = 0.06 ± 0.015 for acrylonitrile - vinyl trichloroacetate (VTAc). The penultimate model of the copolymerization and the effect of the vinyl chloroacetate structure were discussed.
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  • 6
    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-1502) loaded with 50 phr carbon black (HAF) was prepared. The electrical conductivity of rubber vulcanizates was measured. It was found that milling conditions have a marked effect on the temperature dependence of the electrical conductivity σ(T) of test samples. In this case, the resistivity of prepared samples increases with remilling and has a minimum value on the σ(T) curve. Thermal-oxidative aging of such vulcanizates decreases the conductivity of the prepared samples.
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  • 7
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Styrene, methyl acrylate, and N,N-dimethylacrylamide were copolymerized with small proportions of p-nitrophenyl acrylate or p-nitrophenyl esters of CH2=CHCONH(CH2)nCOOH (n = 1,3,5). The aminolysis of these copolymers in dioxane and chlorobenzene solution was compared with the corresponding reaction of low molecular weight analogs. The ratio of the reactivity of the polymer substituent and its analog was found to be insensitive to the nature of the amine but strongly dependent on the nature of the polymer backbone. Poly(dimethylacrylamide) chains carrying active ester substituents were in some cases much more reactive than their analogs due to the activating effect of the dimethylamide groups. In the case of the p-nitrophenyl acrylate-styrene copolymer, the aminolysis exhibited a dispersion of the rate constant due to its sensitivity to stereoisomerism in the vicinity of the active ester, but no similar effects were observed with the other copolymers.
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  • 8
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 165-183 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The differences in the porous and crystalline structure of cell walls in never-dried and nature-dried cottons have been examined by measurements of dye adsorption and desorption, centrifugal liquid retention, and decrystallization due to swelling in sodium hydroxide. Equilibrium dyeings of these two cottons have been carried out at 50 and 60°C with two direct dyes, Chlorazol Sky Blue FF and Chrysophenine G, and the adsorption isotherms obtained. The dye uptake at limiting saturation is found to be quite large for never-dried cotton as compared to nature-dried cotton, indicating a larger number of sites available to dye molecules in the former sample. However, dyeing parameters such as affinity and differential heat of dyeing are found to have lower values for never-dried cotton. This is attributed to the “frozen” structure of a large amount of water held by never-dried cotton, which retards the adsorption of dye molecules. Studies on retention of liquids (glycerol and water) by cotton by use of centrifugation techniques reveal a larger amount of pore volume in never-dried cotton than in nature-dried cotton. X-Ray studies on decrystallization of cotton by swelling in NaOH indicate that the phase transformation to cellulose II in never-dried cotton is complete at 25% (w/w) concentration of NaOH, whereas under identical swelling conditions about 10% residual, unconverted cellulose I is found in the case of nature-dried cotton. A somewhat similar anomaly is found in the dye desorption measurements. Under conditions when the dye can be completely stripped from nature-dried cotton, the never-dried cotton has been shown to retain about 50% to 80% of the adsorbed dye. These observations are attributed to irreversible pore closure during drying of never-dried cotton. Structural collapse occurring during drying of never-dried cotton, after subjecting it to solvent exchange with a large number of organic liquids, was studied by x-ray diffraction, optical microscopy, and centrifugal liquid retention techniques. It was demonstrated that the structural collapse is proportional to the polarity of the organic solvent employed in the final exchange of never-dried cotton, prior to drying. It is concluded that the structural collapse and the development of inaccessible zones in fiber during drying can be reduced if the water in never-dried cotton is exchanged with a nonpolar solvent.
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  • 9
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 203-218 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of MMA was kinetically studied in the presence of visible light (using a 125-W high-pressure mercury vapor lamp with fluorescent coating, without a filter), a THF - bromine charge-transfer complex being used as the photoinitiator. The initiator exponent was 0.5 in bulk polymerization. The monomer exponent varied from about 1.2 to about 2.5, depending on the nature of the solvent used; the initiator exponent also varied in diluted systems, depending on the nature and proportion of the solvent, the variation being from a value of 0.5 in bulk system to zero or almost zero at about 25% (v/v) solvent concentration. Other kinetic parameters, viz., kp2/kt and the activation energy for polymerization, were determined and are reported. Kinetic and other evidence indicates that the photopolymerization takes place by a radical mechanism and termination is bimolecular in nature in bulk systems; in dilute systems, termination by initiator complex assumes predominance, particularly at high solvent concentrations (≥25% v/v).
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  • 10
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 427-432 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The molecular mobility in an interpenetrating polymeric network (IPN) based on crosslinked polyurethane (1) and styrene-divinylbenzene copolymer (2) was studied by broad-line NMR spectroscopy and reversed gas chromatography. NMR and infrared investigations show the absence of chemical interaction between the two constituent networks. For an IPN in the temperature range -196 to 120°C transition regions corresponding to the individual networks and to an intermediate region were found, the latter being characterized by an additional transition at 25-60°C (NMR spectroscopy) and 44-78°C (gas chromatography). The existence of an intermediate region, presumably of loosely packed structure, leads to a shift in the beginning of the temperature transition in IPN to lower temperature and to a decrease in activation energies of relaxation in comparison with the individual networks. The activation energies in IPN are decreased with increasing weight fraction of the second network.
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  • 11
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 433-439 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The published Coulter Counter method for measuring particle size distribution of the discrete phase in rubber-modified polystyrene is shown to be subject to serious limitations, especially when the data generated are used to compute discrete phase volume fractions. The source of error is time-dependent swelling of the particles in DMF which is used to isolate them from the polystyrene matrix for the counting operation.
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  • 12
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 441-444 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An improved Coulter Counter procedure is described for determining the size distribution and volume fraction of the elastomeric discrete phase in high-impact polystyrene. The method isolates the discrete phase from a dispersion of the whole polymer in DMF by centrifugation and redisperses the discrete phase in an aqueous surfactant solution, thus allowing the particles to deswell and resume the dimensions they had in the polystyrene matrix. By measuring a Coulter Counter size distribution on the aqueous dispersion, a discrete-phase volume fraction can be reliably derived for the original impact polystyrene. The method is rapid and precise.
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  • 13
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 445-450 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of triplet sensitizers, benzophenone and anthraquinone and metal acetylacetonates [Co(II, III), Cu, Sn, and Ni] on the photodegradation of polyurethane was examined. Ultravioletvisible (UV-V) absorption spectra, gel formation, and luminescence emission of the polymer before and after irradiation were measured. Changes in UV-V absorption of the polymer and the formation of an insoluble fraction in the polymer were accelerated in the presence of the triplet sensitizers, and (Co(II, III)), Cu, and Sn acetylacetonates. Unirradiated polyurethane was excited by irradiation at 290 and 346 nm, and emitted light at 310 and 420 nm. After 1/2 hr irradiation emission of luminescence was observed at 430 nm, excitation at 290 and 346 nm; after 2hr irradiation at 530 nm, excitation at 420 nm was observed. The results suggest that photodegradation of the polyurethane proceeds via excited triplet states forming excimer between the polymers at the initial stage and exciplexes between the polymer and degradation products or intermediates after a certain irradiation.
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  • 14
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 451-460 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(vinyl alcohol) (PVAI) was oxidized by ceric ion, Ce(IV), in aqueous HNO3 medium at different temperatures and found to be degraded as a result of selective cleavage of the 1,2-glycol unit existing in PVAl. The rate of oxidation increased with increasing temperature. The aldehyde groups formed at the ends of the degraded polymer upon oxidation were relatively stable at 0°C. With rise of temperature, the aldehyde groups reacted either with excess of Ce(IV) to carboxylic acids or with hydroxyl groups of PVAl molecules to give acetal linkage. When the acetalization predominated over the oxidation to carboxyl group, gelation of the reaction mixture was observed. Based on these results, a plausible mechanism of oxidation of PVAl with Ce(IV) and the subsequent reactions is discussed.
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  • 15
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 461-467 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A process for the chemical modification of polybutadienes and natural rubber by various metallocene compounds is described. Soluble products of up to 43% ferrocene content were obtained. The effect of substrate, metallocene, and reaction conditions on the course and extent of substitution was investigated. The glass transition temperature Tg was found to increase considerably with the degree of substitution, e.g., cis-polybutadiene substituted with ferrocene (18 mole-%) has a Tg of 30°C, as compared with -91°C for the unsubstituted polymer.
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  • 16
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 469-488 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The diffusion-free radiation graft polymerization of styrene onto polyethylene has been studied. The grafting rate shows a dependence on monomer which is far different than what has been assumed. Further, the dependence on monomer changes with increasing dose rate as does the dependence of grafting rate on radiation dose rate. Three different regions of behavior are defined: (1) a region of low dose rate where the grafting rate is 1/2-order in dose rate and 3/2-order in monomer; (2) a region of intermediate dose rate where the grafting rate is intermediate between 1/2-and zero-order in dose rate and 5/2-order in monomer; and (3) a region of high dose rate, where the grafting rate is independent of dose rate and at least 5/2-order in monomer. Various possible mechanisms responsible for these effects are discussed, including the effects of viscosity on the initiation and termination reactions, the possibility of ionic graft polymerization, and energy transfer.
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  • 17
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 499-505 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of MMA initiated by a system of α-amylase, cupric chloride, and water was carried out. The effects of the amounts of water, copper(II) ion, and MMA on the conversion of MMA were studied. The overall activation energy was estimated to be 55 kJ/mole. Urea, known as a denaturing agent for protein, was found to increase the rate of polymerization and efficiency of grafting onto α-amylase.
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  • 18
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 507-511 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The molecular weight distribution in thermal polymerization, for which the termination rate is comparable with the transfer rate, is analyzed by assuming that (1) the termination rate is independent of chain length; (2) the rate is translational diffusion-controlled; and (3) the rate is influenced by the excluded volume. The theoretical distribution, based on the assumption that the rate is translational diffusion-controlled, is the best fit to the experimental data at high temperature. The dependence of the rate on chain length is stronger at higher temperature (〉80°C). The ratio of the termination rate to the transfer rate increases with increasing temperature.
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  • 19
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 489-497 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Laser-probe pyrolysis is used to investigate the synergistic flame-retardancy effect observed for antimony oxide (Sb2O3)-PVC combinations. Molecular beam-mass analysis detection techniques permit direct sampling of the laser-vaporized species without the need for intermediate product collection stages. Laser pyrolysis of a PVC formulation containing 3 phr Sb2O3 provides the first direct evidence for the production of volatile SbCl3 during thermal decomposition. Selective laser irradiation of PVC in the presence of unheated Sb2O3 in the sample cell reveals that HCl evolved from the polymer substrate rapidly reacts with Sb2O3(s) to form the volatile flame-retardant species SbCl3. Similar results are observed for SbOCl(s). These reactions are distinct from those previously proposed, which involve the formation and subsequent thermal decomposition of intermediate solid-phase antimony oxychlorides, and demonstrate that the antimony compounds, rather than serving only as inert sources for SbCl3, readily participate in direct chemical reactions with HCl. In addition to the composition of the reaction products, information is also obtained on their evolution characteristics from the sample cell.
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  • 20
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 513-519 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 21
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 647-658 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to obtain quantitative results on the mechanism of ring-opening polymerization of ethylene oxide, 13C satellite spectra of dideuterioethylene oxides and their polymers prepared by anionic, cationic, and coordination catalysts were measured with deuterium decoupling and analyzed. The ratios of the threo to erythro polymers were same as those of the cis to trans monomers. Therefore, it is concluded that the ring-opening polymerizations of ethylene oxide proceed almost entirely with inversion of configuration, confirming the results obtained by the analysis of the infrared spectra of the deuterated polymers by Price, Tadokoro and co-workers.
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  • 22
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 675-681 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A survey has been made of the polymerizability of diallysilanes, including a number of new compounds. Rates of polymerization are generally low with radical or Ziegler-Natta techniques, but excellent yields are often obtained when the initiator is aluminum bromide.
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  • 23
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 659-673 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Anionic polymerization of 2-vinylpyridine has been studied, initiated either by dialkyl and diaryl magnesium or by living oligomers in tetrahydrofuran solution at 20°C. Spectrophotometric observations indicate the existence of stable active species with different structures. Kinetic data for propagation and viscosimetric measurements on two-ended polymers agree with a cyclic structure of living polymers and lead us to the conclusion of the existence of reactive negative “tripleions.”
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  • 24
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photosensitized crosslinking of polyenes with polythiols has been demonstrated to be a free-radical chain reaction whose apparent quantum yield is in the range of 2 × 102-4 × 102 mole/einstein. Initiation occurs by abstraction of a hydrogen atom from the thiol group by the excited n,π* triplet of the ketonic photosensitizer. Kinetic studies of model systems have shown that electron-donating substituents attached or close to the double bond accelerate the thiol addition while electron-withdrawing groups decrease the rate. With a given olefin, slight differences in reaction rates are observed depending on the structure of the thiol. Mercaptopropionate esters are more reactive than mercaptoacetates which, in turn, are more reactive than alkane thiols. Cure rates for polyene-polythiol systems are in accord with results found for the model systems. Aromatic carbonyl compounds are the most effective sensitizers for this reaction. To a first approximation, the effectiveness of the sensitizer depends only upon the absorbance. No correlation was found between photoactivity and the triplet energies or lifetimes of the sensitizers.
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  • 25
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 799-813 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of γ-initiated oxidation of solid poly(ethylene oxide) (PEO) has been investigated, and an overall reaction scheme has been developed which accounts for most of the experimental observations. Data are correlated on the basis that the oxidation process is the sum of two reactions that are first-order and half-order in rate of initiation. They provide evidence that a significant fraction of the interactions of α-alkoxyalkylperoxy radicals is nonterminating at ambient temperature and yield free alkoxy radicals that are very subject to β scission. The unimolecular decomposition of secondary peroxy radicals, which has been invoked previously for the oxidation of PEO in solution, is not needed to explain the products of the oxidation of PEO in the solid phase. Approximately 90% of the total oxygen consumption has been accounted for by the observed products of oxidation. The radiochemical yield for backbone radical formation in irradiated PEO was estimated to be 6.5 ± 1.5.
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  • 26
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Optical properties and conformations, in solution, of optically active polyamides derived from (+)(S)-trans-1,2-cyclopropanedicarboxylic acid with secondary diamines such as trans-2,5-dimethylpiperazine (DMPIP), piperazine (PIP), or N,N′-dimethylethylenediamine (DMED) have been investigated and compared with the corresponding diamide model compounds. The results suggest that the rigid DMPIP and PIP polyamides may exist in ordered conformations in 2,2,2-trifluoroethanol (TFE) and tetramethylene sulfone (TMS), while reversible conformational transitions to highly extended forms may be induced by the addition of methanesulfonic acid (MSA). In MSA/TMS mixtures, a change in the optical properties, and thus possibly in the conformations, can be observed around 0.5 mole fraction of MSA. A study of CD at higher temperature indicates that the conformations of the DMPIP and PIP polymides tend to be randomized on heating in TMS and probably also in MSA. No evidence for salt effects on conformation has been observed. Possible ordered conformations have been proposed.
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  • 27
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 837-845 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ESR spectra of γ-irradiated poly(methyl methacrylate) (PMMA) at 77°K and the effect of additives have been studied. γ-Irradiation of PMMA containing a small amount of 2-methyltetrahydrofuran as an additive at 77°K gives MTHF radical. Yields of MTHF radical increase with increasing MTHF concentration and reach a plateau value, and are independent of photobleaching with visible light. Yeilds of polymer radical are reduced by the addition of MTHF. Some elementary processes for the MTHF radical formation are proposed on the basis of the experimental results.
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  • 28
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 829-835 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 3-formyl-2-pyrazolines (pyrazoline-3-carboxaldehyde) obtained by 1-3 dipolar additions of diazoesters to acrolein are unstable and smoothly polymerize through the aldehyde group to a polyacetal polymer. On the basis of spectroscopic data, this paper describes the structure of the isolated polymers, along with their properties and a polymerization mechanism. It is proposed that a nucleophilic attack of an heterocyclic amino nitrogen on another monomer formyl group leads to an internal ion pair, and that this latter promotes a polycondensation of other aldehydic units according to an anionic type of propagation. The results are polyacetal polymers of low molecular weight with conservation of the heterocyclic framework. However, numerous side reactions are possible and account for the relatively low molecular weights observed.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 847-851 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cis-(S)(+)-2-phenylvinyl alkyl thioethers having 1-methylpropyl (I), 2-methylbutyl (II), and 3-methylpentyl as alkyl groups, were prepared by condensation of phenylacetylene with sodium thioalcoholates in the presence of sodium ethoxide. Thioethers I, II, and III did not polymerize with radical initiators but could be polymerized cationicaly with BF3·Et2O or SnCl4 in bulk at room temperature to oligomers with molecular weights about 2000. Specific rotations of polymers were compared with those of phenylethyl alkyl thioethers, and it was found that there was no difference in the rotation of polymers having molecular weights up to 2000 and model compounds.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 853-864 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyenes formed in the thermal degradation of PVC are readily oxidized in the liquid phase in the presence of a radical initiator. In pure oxygen at a constant rate of initiation, different length polyenes are consumed by a first-order reaction: the rate of consumption is proportional to the polyene length and to the square root of initiator concentration. Applying the relationships given by the theory of chain reactions, we determined the ratio of the rate constant of chain propagation calculated for one double bond k2 to the square root of the chain-termination rate constant k4. The value obtained, which is relatively high in comparison to other unsaturated hydrocarbons, reflects very well the high reactivity of polyenes of the degraded PVC sample towards oxidation. Intramolecular chain propagation steps are also likely to play a role in the oxidation of polyenes.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 865-873 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ring-opening polymerization of unsubstituted lactones by Al2—Zn and Al2—Co(II) μ-oxoalkoxides in homogeneous organic phase is described. Under these conditions, the chain propagation is very fast and proceeds without transfer or termination reactions. The composition and structure of the main products resulting from the first polymerization steps have been determined, and fit with a monomer insertion mechanism into the aluminum-alkoxide bonds of the catalyst.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 875-895 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A kinetic study of ethylene oligomerization in hexane, in the presence of n-BuLi-TMEDA complexes, allowed us to suggest a new mechanism for anionic ethylene oligomerization. n-BuLi and n-Bu(CH2CH2)Li species have the same reactivity. The RLi-TMEDA complex in a 1-to-1 stoichiometry is the active species. The following kinetic equation has been established: \documentclass{article}\pagestyle{empty}\begin{document}$$ V_p = k_p K_D ^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} \left[ {\left( {{\rm BuLi} - {\rm TMEDA}} \right)_2 ^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} } \right]\left[ {{\rm Et}} \right] $$\end{document} It reflects the intervention of associated species (n-BuLi-TMEDA)2 as well as the influence of the concentration of the complexing agent on the kinetics of oligomerization.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 973-981 
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    Topics: Chemistry and Pharmacology
    Notes: Linear D2-m-carborane-siloxanes with one, two, and three trifluoropropyl moieties per repeat unit were prepared by the condensation reaction between bisureidosilanes and carborane disilanol. Molecular weights between 100,000 and 220,000 were obtained. Compared to fluorosilicones, the trifluoropropyl-modified carborane-siloxanes exhibited greater thermal and oxidative stability and in certain cases comparable solvent resistance. The swelling index for carborane-siloxane elastomers decreased with increasing trifluoropropyl content, although this fluorocarbon moiety did compromise the thermal stability of the carborane system.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 983-989 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: A new solvent system comprising a mixture of nitrobenzene and tetrachloroethane has been developed for determining the molecular size distribution of poly(ethylene terephthalate) (PET) by gel-permeation chromatography (GPC). Unlike hot m-cresol, which until now has been the standard GPC solvent for PET, the nitrobenzene-tetrachloroethane mixture can be used at room temperature and thus minimizes polymer degradation and distribution equilibration. Results with this new system reveal reproducibly discernible differences between PET samples prepared by melt and solid-state polymerization, differences not previously noted in GPC reports based on the use of m-cresol.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1027-1028 
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    Keywords: Physics ; Polymer and Materials Science
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1021-1025 
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    Keywords: Physics ; Polymer and Materials Science
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 991-1019 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Surfaces of polymers [polyethylene, polystyrene, poly(ethylene terephthalate), poly(oxymethylene), cellulose acetate, polyacrylonitrile, nylon 6, and polytetrafluoroethylene] treated with argon (inert) and nitrogen (reactive) plasma were examined by ESCA (electron spectroscopy for chemical analysis). Argon plasma treatment generally introduces oxygen functionalities into the polymer surface. Nitrogen treatment generally incorporates nitrogen and oxygen functionalities into the treated surface. The extent of oxygen incorporation is typically less than that produced by argon plasma. When nitrogen and oxygen functional groups are already in a polymer structure, the extent of additional incorporation of these two elements as a result of plasma treatment is very much less than with other polymers. Polymers which contain only one of the elements tend to incorporate the other element to much the same degree as polymers without either element initially present.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1029-1033 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: A method has been developed for the calculation of elementary rate constants of deceleration and acceleration reactions on polymers in which the reactivity of the group is influenced only by the character of the closest adjacent groups. It is suggested that this method may be valid if the calculation yields a rate constant k′3, which is independent of conversion. In this case, the sequence analysis of products can be performed by using Markovian first-order statistics, and the rate constants thus obtained can be used for calculating the relative frequencies of variously long sequences of reacted and unreacted groups and their number-average length. For markedly accelerated reactions, a simplified method of estimation of the average sequence length involving use of two of the three elementary rate constants, i.e., k1 and k′2, has been suggested.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1035-1041 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The fast and living ring-opening polymerization of lactones by bimetallic μ-oxoalkoxides in homogeneous organic phase has led to successful block copolymerization. The catalyst is coordinatively associated in organic media; however, interaction with lactones can induce, following their nature, different rearrangements of the catalytic aggregates, depending on the nature of these lactones. Consequently, ε-caprolactone and β-propiolactone block copolymers are quantitatively obtained only in the presence of a completely dissociated catalyst.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1043-1060 
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    Topics: Chemistry and Pharmacology
    Notes: Regular copolyoxamides were prepared from diamine-oxamides and aliphatic diacid chlorides by interfacial and solution polymerization. Interfacial polymerization is preferred with diamineoxamides where the diamine portion has two to six methylene groups and the diamine-oxamides are readily soluble in water. Regular aliphatic polyoxamides from diamine-oxamides are readily soluble in water. Regular aliphatic polyoxamides from diamine-oxamides with more than six methylene groups in the diamine portion of the molecule are better prepared by solution polymerization in dimethyl acetamide. Regular aliphatic oxamides are soluble in trifluoroacetic acid and hexafluoroisopropanol and show a considerable alternation of the melting point behavior in the diamine portion of the polyamides with up to five methylene groups. Copolyoxamides with two and four methylene groups melt higher than the copolyoxamides with three and five methylene groups. Aliphatic copolyoxamides/adipamides melt at approximately 260°C and show a steady decrease in melting points to about 220°C for polyoxamides with twelve methylene groups.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1061-1071 
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    Topics: Chemistry and Pharmacology
    Notes: Optically active α-(p-substituted benzenesulfonamido)-β-lactones having as para substituents OMe, Me, H, and Cl were polymerized in bulk, in ethyl acetate solution with triethylamine or betaine, and in dioxane with butyllithium as initiators. The rate of polymerization was followed by the change of specific rotation with time and was decreasing in following order of para substituents: OMe 〉 Me 〉 H 〉 Cl. The relative reactivity in logarithmic form was plotted against Hammett's σ functions showing a linear relationship with reaction constant ρ = -0.57.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1073-1079 
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    Topics: Chemistry and Pharmacology
    Notes: The electron spin resonance (ESR) spectra of polymer radicals found to be trapped in polytetrafluoroethylene (PTFE) polymerized with radical initiators were comparatively examined under various conditions and assigned. They are identified as the primary (propagating) radicals RCF2CF2·, which are transformed to primary peroxy radicals RCF2CF2OO· in the atmosphere. Studies of the rates of polymerization and postpolymerization and ESR measurements indicate that the radical content steadily increases during polymerization. The results are discussed in connection with the mechanism of polymerization of tetrafluoroethylene (TFE) and the unusual thermal stability of these radicals in PTFE prepared with initiator.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1155-1167 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal degradation of the monomer and polymer of bis(p-toluenesulfonate) of 2,4-hexadiyne-1,6-diol has been investigated. Decomposition during the latter stages of solid-state thermal polymerization at 80°C and of 100% polymer at 112°C was observed by mass spectrometry and the decomposition fragments identified. Mechanisms for this low-temperature degradation are suggested. Pyrolysis of the monomer and polymer between 400 and 1000°C was studied by gas chromatography and mass spectrometry. The principal pyrolysis products are triacetylene and p-toluenesulfonic acid. The fragmentation routes leading to and derived from these products are discussed.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1189-1197 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Insoluble polysalt complexes are formed on mixing aqueous solutions of poly(vinylbenzo-18-crown-6) (P18C6) and sodium carboxymethylcellulose (CMC) in the presence of certain salts. Potassium salts are especially effective, converting the neutral P18C6 into a polycation which then interacts with sodium CMC. Nearly quantitative precipitation can be achieved at low KCl concentration (ca. 0.005M) for a crown/carboxylate ratio of approximately 5, while for 0.1-0.2M KCl the precipitation is close to completion at a crown/CMC ratio of about 2. The precipitates solubilize again on addition of water or concentrated KCl. Precipitation also occurs with CsCl but not with NaCl. Potentiometric measurements were carried out to determine the complex formation constant of the three alkali ions to P18C6. Their values can be used to rationalize the observed phenomena. Charge equivalence appears to play an important role in the formation of the polysalt complexes.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1239-1254 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Some new polymers and model compounds were obtained from the reaction of N,N-protected glutamic anhydride with primary amines and the ring-opening reaction was proved to belong to γ-orientation. When the primary amine is aromatic ortho-diamine, it was proved that the reaction route of ring-closure dehydration of the ring-opening addition products was through imidazolecarboxylic acid rather than imide amine, and at the last step it becomes imidazopiperidone. The corresponding polymer containing pyromellitdiimide and benzimidazopiperidone in the main chain was synthesized by a three-step reaction of 2,2′-pyromellitdiimidodiglutaric anhydride with 3,3′-diaminobenzidine. In the first step, polyaminoamic acid having pyromellitdiimide ring was prepared in polar solvents. In the second step, the conversion of polyaminoamic acid to the copolyimidoimidazole acid was carried out thermally in solution or solid at 140-200°C. At last, the conversion of copolyimidoimidazole acid to the copolypyromellitimidobenzimidazopiperidone was performed either thermally (300°C) or by chemical means. Infrared spectra and NMR spectra were studied and compared with corresponding model compounds. Form solubility and TG analysis, the polymer belongs to a heat-resistant polymer.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1225-1238 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: When heated in solution at about 160°C, pyridine quaternary salts of bromomalonamides lose 1 mole of cyanic or isocyanic acid almost quantitatively in a manner quite analogous to the decarboxylation of an acid. By DTA and DSC, the crystalline salts are stable up to their melting points (〉220°C) at which temperatures concurrent fusion and decyanation processes occur (endotherm); these are immediately followed by an exotherm related to the trimerization of cyanic acid. TGA measurements on the solid salts do not clearly define the loss of 1 mole of cyanic acid because in the solid state, thermal decyanation is accompanied to some extent by other pyrolytic reactions. Preparative methods for quaternizing poly(4-vinylpyridine) with bromomalonamide are described and two polymeric quaternary salts (33 and 100% substituted) were prepared and analyzed. These polyelectrolytes are water soluble and upon the addition of base the yellow polymeric nitrogen ylids are generated. Infrared spectra on the polymeric quaternary salts and visible spectra on the polymeric ylids are included. The ylid chromophore has an ε = 1800 at λmax = 415 nm. The dilute solution viscosity behavior of these polymers in H2O and in 0.05N KBr is typical of polyelectrolytes. Both polymers in dilute solution show a maximum in ηsp versus pH plots. In water, the viscosity of these polymers decreases with time, and it is proven that this results from a conformational change which accompanies amide hydrolysis rather than polymer backbone degradation. Glass transitions are not detectable by DTA but both polymers show well-defined trimerization exotherms for cyanic acid starting at 170-175°C. Thus, decyanation of the solid polymeric quaternary salts is more analogous to decyanation of the crystalline quaternarys in solution than as solids. TGA measurements on the polymers show weight losses which are of the correct order of magnitude and in the correct temperature range for monodecyanation. Some data are presented which suggest that perhaps a second mole of cyanic acid is lost at about 250°C. Quaternization of poly(4-vinylpyridine) with bromomalonamide reduces its gross decomposition temperature from 385°C to about 285-317°C. It is demonstrated how thermal decyanation can be used for the in situ generation of cyanic acid for the modification of organic compounds. The preparation of a partial urethane of poly(vinyl alcohol) using this method is described. We have also shown that aliphatic quaternary salts can be prepared and that they too undergo the decyanation reaction.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1289-1289 
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    Keywords: Physics ; Polymer and Materials Science
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1431-1439 
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    Topics: Chemistry and Pharmacology
    Notes: High molecular weight alternating ethylene-ethyl acrylate copolymers were prepared by using boron trifluoride to complex the acrylate ester. The polymerizations were run under mild conditions (25-50°C, 6-20 atm ethylene) in dichloromethane or dichloroethane solution with free-radical initiation. At lower ethylene pressures or at less than stoichiometric levels of BF3, the polymers are acrylate-rich. This is due to ethyl acrylate homopolymerization competing with the copolymerization reaction. The effect of other polymerization variables is also discussed.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1473-1478 
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    Topics: Chemistry and Pharmacology
    Notes: 2-Hydroxypropyl methacrylate has been copolymerized with methyl acrylate, ethyl acrylate, n-butyl acrylate, and methyl methacrylate in bulk at 60°C using benzoyl peroxide as initiator. The compositions of copolymers have been determined by the estimation of the hydroxyl group by acetylation process. The copolymerization parameters have been determined by conventional scheme of copolymerization.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1479-1487 
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    Topics: Chemistry and Pharmacology
    Notes: Photodegradation of carbon monoxide-styrene copolymer in benzene was investigated. In relation to the average number of main-chain scissions per macromolecule versus photoirradiation time, the straight line did not pass through the origin. This phenomenon was attributed to the presence of a labile bond from the carbonyl group in the main chain, in accordance with the results of Cameron and Lawrence which were found in the study of photodegradation of thermally polymerized polystyrene. In utilization of photodegradative behavior in carbon monoxide-styrene copolymer, a block copolymer of styrene with methyl methacrylate was prepared and was ascertained by precipitated fractionation, elementary analysis, and turbidimetry.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1499-1502 
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1503-1506 
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1489-1498 
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    Topics: Chemistry and Pharmacology
    Notes: The effect of the alkyl group on the relative reactivity of a homologous series of vinyl esters (2) has been studied with ethylene (1) as reference monomer, tert-butyl alcohol as solvent, at 62°C and 35 kg/cm2. The experimental method was based on frequent measurement of the monomer feed composition throughout the copolymerization reaction by means of quantitative gas-chromatographic analysis. Highly accurate monomer reactivity ratios were estimated in a statistically justified manner by a nonlinear least-squares method applied to the integrated copolymer equation. The reactivity of the vinyl ester monomers towards an ethylene radical increased with decreasing electron-with-drawing ability of the ester group. All vinyl ester radicals considered turned out to have the same preference for their own monomer over ethylene (constant r2 = 1.50). Reactivity ratios are discussed in terms of the Q-e scheme and the Taft relation. It appeared that chiefly polar factors contribute to the observed relative reactivity, while probably resonance stabilization only plays a minor part. Steric hindrance seems to impair monomer reactivity, only from vinyl pivalate on. Relative reactivities of the vinyl esters are compared with literature values, where other reference monomers have been used.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1507-1509 
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1517-1518 
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1511-1516 
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1523-1526 
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1519-1521 
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1541-1542 
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1573-1583 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to determine the stereoregularity of poly(4-vinylpyridine), 4-vinylpyridine-β,β-d2 was synthesized from 4-acetylpyridine. The 1H-NMR spectra of the deuterated and nondeuterated polymers were measured and analyzed. From the 1H-NMR spectra of poly(4-vinylpyridine-β,β-d2), triad tacticity can be obtained, while the 1H-NMR spectra of nondeuterated poly(4-vinylpyridine) give the fraction of isotactic triad. The 13C-NMR spectra of poly(4-vinylpyridine) were also observed, and the spectra of C4 carbon of polymers were assigned by the pentad tacticities. The fraction of isotactic triad of poly(2-vinylpyridine) and poly(4-vinylpyridine) obtained under various polymerization conditions were determined. The radical polymerization and anionic polymerizations with phenylmagnesium bromide and n-butyllithium as catalysts of 4-vinylpyridine gave atactic polymers.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1585-1593 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A solvent-soluble polybiphenylene with a single hetero atom in the chain (a bridged polybiphenylene) was prepared according to the synthetic procedure for a solvent-soluble poly(4,4′-biphenylene). In addition, a related copolymer was similarly prepared by the addition of the MMA monomer in the reaction system. The thermal properties and viscosity behavior of each product were influenced by the hetero atom, especially by the introduction of MMA component in the chain. Each viscosity curve (ηsp/c vs. c) shows an anomalous peak at a specific concentration (0.3-0.002 g/100 ml DMF), depending upon the atomic group. The ηsp/c value for each homopolymer was not over 0.1 except in the neighborhood of the anomalous peak, while those for copolymers became 3-4 times larger than values for corresponding homopolymers. It is obvious that the viscosity of each copolymer increases due to an increase in flexibility due to introduction of the MMA units in the chain, since little difference in molecular weights is found between homopolymers (16,000-15,000) and copolymers (10,000-12,000).
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1595-1602 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactivity ratios for various acrylonitrile-phenyl acrylate systems have been determined for radical copolymerization at 60°C in dimethylformamide. The values of the ratios calculated by the linear graphical method of Kelen and Tüdös were as follows: r1 = 0.46 ± 0.02 and r2 = 0.36 ± 0.04 for acrylonitrile-phenyl acrylate, r1 = 0.73 ± 0.02 and r2 = 0.80 ± 0.02 for acrylonitrile-p-cresyl acrylate, r1 = 0.33 ± 0.03 and r2 = 0.9 ± 0.02 for acrylonitrile-p-chlorophenyl acrylate, r1 = 0.82 ± 0.03 and r2 = 1.02 ± 0.03 for acrylonitrile-p-bromophenyl acrylate, r1 = 1.12 ± 0.05 and r2 = 1.16 ± 0.05 for acrylonitryle-o-chlorophenyl acrylate, and r1 = 1.26 ± 0.05 and r2 = 0.86 ± 0.05 for acrylonitrile-m-chlorophenyl acrylate. The dependence of reactivities of the monomers upon their chemical structure was discussed.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1619-1628 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radiation-initiated graft polymerization of styrene onto polyethylene was studied to determine whether energy transfer to diluent was responsible for the previously observed high orders of dependence of the grafting rate on monomer concentration. n-Octane was used as the diluent instead of benzene. If energy transfer from excited polyethylene to benzene were present, it should not be with n-octane. The percent swelling of polyethylene by various n-octane-styrene mixtures was determined. The compositions of various n-octane-styrene mixtures absorbed inside polyethylene were determined by ultraviolet and refractive index measurements and found to be richer in styrene than the corresponding mixtures in which the polyethylene had been placed. The graft polymerization rates were determined at 0.000761, 0.0371, and 0.213 Mrad/hr and plotted against the inside styrene concentrations on a log-log scale to yield the kinetic orders of dependence of rate on monomer as 2,3, and 3, respectively. It was concluded that energy transfer to diluent was not responsible for the high-order dependence observed.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1637-1644 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of novel photodegradable poly(o-nitrobenzaldehyde acetals) is described. The polymers were prepared by condensing o-nitrobenzaldehyde with a series of glycols. Polyesteracetals can also be prepared by first preparing the o-nitrobenzaldehyde glycol acetal or polyacetal prepolymer and subsequent reaction with a diacid chloride. These polymers, although light sensitive, appear to be thermally stable since they were prepared in part by melt condensation techniques. The polymers are useful as positive working photodegradable polymers.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1765-1772 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A short review of the effect of pressure on copolymerization kinetics shows the necessity of simple models for a better understanding of activation volumes. Therefore, a simple concept, possibly generally valid for free-radical polymerization, is proposed, based on the assumption that molar volumes of activation can be expressed as an addition of a characteristic radical and a monomer contribution, regardless of the combination involved. The scheme may facilitate the visualization of the transition state and contribute to the understanding of reaction mechanisms of radical polymerizations. Ethylene-vinyl acetate copolymerization at 62°C with tert-butyl alcohol as solvent agrees with the proposed scheme, appearing from the pressure independence of the product of reactivity ratios at the different levels (35,600, and 1200 kg/cm2). Implicitly it can be shown that an ethylene monomer contributes about 2 cm3/mole more to the activation volumes of the propagation reactions than does the vinyl acetate monomer, whereas for the radicals the difference of the respective contributions to the activation volumes is opposite in sign.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1777-1778 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1779-1783 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1811-1818 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photochemical response of two thick photodielectric holographic recording systems was studied by using a 488 nm argon laser line. These systems are made of poly(methyl methacrylate) or poly(methyl α-cyanoacrylate) with p-benzoquinone as sensitizer. It was found that in both systems, photochemically induced branching, followed by crosslinking of the polymeric chains provide the major effects that modulate the index of refraction of these materials. The change in polymer structure as measured by intrinsic viscosity was correlated to the change in index of refraction, by which the holographic recording process is accomplished.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1799-1810 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Analysis by 250-MHz proton magnetic resonance (PMR) allows more precise examination of the microstructure of anionic polyisoprenes and polybutadienes obtained in the presence of organo-alkali metals. Besides vinyl addition, the propagation of contact ion pairs in dioxane solvent gives a mixture of cis and trans products with isoprene, whereas only trans product is obtained with butadiene. The presence of 1,4-trans-polyisoprene appears to be inconsistent with the cis configuration of the polyisoprenyllithium living end in dioxane or tetrahydrofurane media. In taking into account the existence of complexation phenomena, it was suggested that propagation mechanisms should involve a transition state which should begin with the trans configuration before isomerization into the more stable cis configuration. For the free ions, the living end of the carbanion should be entirely trans.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1843-1854 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This study is a continuation of previous work done in this laboratory which has demonstrated the possibility of polymerizing built-up monomer multilayers in the solid state. In the present work, the formation, structure, and solid-state polymerization of multilayers of vinyl stearate which can be built up by the method of Langmuir and Blodgett were studied. A new technique to polymerize such films under the water surface was developed. This made possible the formation of poly(vinyl stearate) multilayers with different molecular orientations through bilayer polymerization. The mechanism of deposition and the structure and properties of head-to-tail and head-to-head, tail-to-tail poly(vinyl stearate) multilayers were investigated by using Fourier-Transform infrared spectroscopy, x-ray diffraction, and electron diffraction.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1855-1862 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: High molecular weight poly(ethylene oxalate) with fiber-forming properties was obtained from oxalic acid and ethylene glycol. The process was carried out on two stages in the melt. A new method was used for aliphatic oligoester synthesis in the melt, because the decomposition of oxalic acid takes place in the presence of glycol. The process was carried out at low temperatures with azeotropic water removal. Investigations of the polycondensation of oxalic acid and ethylene glycol with a compound forming a heteroazeotrope with water showed that the process is subject to the general laws of the polycondensation in melt: it depends on the ratio of initial components, presence of accelerating compounds, etc. However, the reaction time of polycondensation was dependent on the stirring intensity. High molecular weight poly(ethylene oxalate) was obtained by oligomer polycondensation in the melt. Thorium carbonate and tin dichloride were used as catalysts.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1863-1868 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A graft copolymer of L-histidine on polyethylenimine has been demonstrated to be an efficient catalyst for the hydrolysis of activated phenyl esters in aqueous systems. A lack of any significant cooperative effects between neighboring imidazoles or amines has been shown by a study of the catalytic solvolysis of p-nitrophenyl acetate at varying pH. A similar study with 4-acetoxy-3-nitrobenzoic acid has displayed a bell-shaped pH-rate profile indicative of electrostatic interactions between the catalyst and substrate. Hydrophobic interactions were also evident from an investigation of the hydrolytic rates of a series of 4-acyloxy-3-nitrobenzoic acids. In an attempt to demonstrate stereospecific catalyzed reactions, the hydrolyses of optically active esters catalyzed by the optically active copolymer were studied.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1869-1881 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Silylation of nonequilibrated phenyl-T-siloxane polycondensates by dimethylchloromethylchlorosilane involves only a small part of the silanol groups present in these prepolymers. At room temperature, silylation and condensation of the silanol groups occur at the same time. This condensation can be either intermolecular only or both intermolecular and intramolecular, depending on the initial condensation state of the prepolymer. It seems that no condensation reactions take place when the reaction is carried out with reflux. In any case, and even with strongly reactive disilazanes, no more than 35% of the silanol groups are consumed. The results give some information about a polymer, the structure of which is (after all) rather badly known.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1883-1888 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetic equations are presented which describe the course of a free-radical polymerization carried to high conversion when chain transfer to monomer or to other low molecular weight agents is important. Calculations are presented which show that the influence of chain transfer to monomer can greatly affect the rate of polymerization and the molecular weight averages when a polymerization is subject to autoacceleration because of the gel effect.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2033-2036 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2037-2040 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2041-2042 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2043-2043 
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    Keywords: Physics ; Polymer and Materials Science
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2047-2057 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The importance of nonexclusion effects in the GPC behavior of several stationary phases was investigated with DMF, 0.01M LiBr, as the mobile phase. Various low MW solutes and narrow MWD polymers, encompassing a wide range of polarities, were studied. The elution of the polymers was examined in terms of “universal calibration” behavior. Styragel and silanized glass both exhibit affinity for apolar polymers in DMF; for the former substrate this effect shows a strong inverse dependence on MW. As a consequence, application of polystyrene calibration curves to GPC analysis of more polar polymers with these substrates leads to overestimations of MW parameters. These errors are not corrected when universal calibration procedures are used. Ideal exclusion chromatography is exhibited by a number of polymers on untreated porous glass substrates. However, polymers with strong hydrogen-bonding functionality appear to be susceptible to marked adsorption in this system.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2059-2065 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oxidation of hydroquinone catalyzed by copper(II) complexes of poly-1-vinylimidazole, vinylamine-vinylacetamide copolymer, and polyethyleneimine was studied in aqueous solution at 25°C. The rate of oxidation was determined spectrophotometrically over several pH values. The rate of copper(II) reduction was evaluated from copper(I)-cuproin complex formation, and the reoxidation of copper(I) to copper(II) was observed by visible spectroscopy. Among the copper(II) complexes, poly-1-vinylimidazole complex exhibited excellent catalytic activity, which amounted to over 20 times that of aqueous copper(II) ion solution, while the reduction of copper(II) in the former system was slower than that in the latter system. The reoxidation of copper(I) to copper(II) was found to be completed immediately in the presence of polymer ligands such as poly-1-vinylimidazole, while copper(I) ion was only slowly reoxidized. The discussion of the reaction mechanism emphasizes the importance of the reoxidation process.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2075-2082 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Crystallization of polyterephthalates of bis(4-hydroxy-3-chlorophenyl)-2,2-propane synthesized by an acceptor-catalytic polyesterification has been investigated quantitatively. It was found that in a homogeneous medium (in solvents for the polymer) amorphous polymers are formed, while polycondensation in a heterogeneous system (in nonsolvents for the polymer) gives rise to crystalline polyarylates, their degree of crystallization being dependent on synthesis conditions. Secondary treatment of resulting polymers can result in their crystallization and amorphization. Along with molecular weight the physicomechanical properties are significantly affected by the preparation method.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2067-2074 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the present work, we use the binary insertion compound LiC12 to polymerize styrene, methyl methacrylate, butadiene, isoprene, and to copolymerize isoprene and styrene in various hydrocarbon solvents (aromatics and aliphatic) and etheral solvents. We show that the styrene polymerization in aromatic solvents gives better yields than in the etheral solvents, the polymer being atactic. Methyl methacrylate does not polymerize in toluene but does so completely in DME. More generally, the yields of polymerization are better with KC37 than with LiC12 because of the different capacities of the monomer to get into the carbon layers. The polymerization of dienes with LiC12 shows that the microstructures of the polymer obtained in π-or n-donor solvents are similar to the ones obtained by homogenous polymerization with Li cation in such solvents. However, for isoprene in cyclohexane, the results are different. The isoprene styrene copolymers are statistical ones and the mean length of styrene blocks is less than 5. The monomer interaction with the insertion compound and the growing chain geometry between the carbon layers are the facts which control either the stereospecificity of the polymerization or the selectivity of the copolymerization.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2083-2095 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Effect of structure of potassium poly(vinyl sulfate) and its homologs on the metachromatic behavior of methylene blue was investigated spectrophotometrically. The metachromatic behavior with addition of polyanions was followed by the changes in the molar extinction coefficient of the 664 nm band of methylene blue and in the wavelength of metachromatic band. Important factors for metachromasy were the number of anionic sites per polymer molecule, the degree of polymerization, and the flexibility of polymer chain. It was found that the amount of KCl or urea required to destroy the metachromasy was a useful measure for estimating the binding strength of methylene blue to polyanions.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2193-2218 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The formation and growth of monodisperse polystyrene latex particles in the absence of added surfactant has been studied by sampling polymerization reactions at different times and determining the surface and bulk properties of the latex. A large number of nuclei in excess of 5 × 1012/ml were generated during the first minute of reaction, but this fell due to coagulation until a constant number (1011-1012/ml) was reached. The rate of polymerization per particle was then found to be proportional to the particle radius. Gel-permeation chromatography has shown that the initial particles consist mainly of material of MW 1000 with a small amount of polymer up to MW 106, and the presence of this low molecular weight polymer, which in many cases can still be detected after 100% conversion, is taken as being indicative of particle formation via a micellization-type mechanism involving short-chain (MW 500) free-radical oligomers. M̄n values determined for the latex particles throughout the course of reactions show that the molecular weight increases to a maximum of about 105 as the particles grow. The presence of anomalous regions within the particles has been confirmed by transmission electron microscopy, scanning electron microscopy, and gas adsorption studies. It has also been found possible to re-expose these regions within apparently homogeneous particles by stirring with styrene monomer; this is indicative of a molecular weight heterogeneity within the latex particles. The presence of sulfate, carboxyl, and hydroxyl groups upon the latex particle surfaces has been determined by conductometric titration.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2239-2253 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Preparations of metal-containing crosslinked polyester resins based on divalent metal salts of mono(hydroxyethyl)phthalate were investigated by the cure, by combined polyesterification and polymerization, of curable mixtures prepared from above metal salts, maleic anhydride, glycidyl methacrylate, and methyl methacrylate. The curable mixtures containing Ca showed lower viscosity than those containing Mg. They were subjected to curing reactions in the presence of peroxide and under photoirradiation, respectively. In the cure, polyesterification and polymerization proceeded simultaneously smoothly, giving metal-containing cured resins. Generally, the peroxide-cured resins showed better physical properties than the photo-cured resins. Especially, the former resins with high metal content showed high compressive strength and Rockwell hardness. Further, resistance to chemical attack and boiling water and thermal behavior are also discussed.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2269-2288 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal oxidative degradation of two aromatic and one segmented polyurethane has been studied, with special emphasis on HCN evolution over a range of temperatures and oxygen concentrations. A tentative mechanism for HCN formation has been presented. Other gaseous products were ascertained by chromatography. Infrared spectra during degradation were measured, and the extent of crosslinking was also determined. It is shown that HCN evolution can be inhibited by copper or its oxide.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2291-2302 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The binding of Cu(II) ions to partly neutralized poly(methacrylic acid) (PMA) has been investigated by potentiometric titration and dialysis to determine the stoichiometry the Cu-PMA complexes formed. Partly ionized PMA was titrated with solutions of the metal ion to enable a large range of metal ion/polymer ratios to be studied. Combination of the results from these two techniques at ionic strength 0.1 indicates that at very low Cu(II)/polymer ratios, a 4:1 complex exists, but at higher ratios the complex breaks down to give a mainly 2:1 coordination with some 1:1 binding. Conductance titrations support these results. Viscometric titrations show strong interactions between the metal and polymer, preventing the full extension of the polyion at high degrees of ionization, and spectrophotometric titrations support the existence of at least two types of complexes in the solution.
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2311-2319 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The presence of anomalous regions within polystyrene latex particles prepared in the absence of added emulsifier has been investigated. It appears that they arise through loss of monomer from particles consisting of a discrete monomer-rich region surrounded by a polymer shell. It is likely that in most cases, monomer is lost from the region on evacuation prior to electron microscope examination, although there is some evidence from γ-irradiated samples (prior to electron microscopy) that loss of monomer can also occur during storage and/or dilution of the sample. Scanning electron microscopy and carbon replication techniques have been used to determine the shapes of the voids. Gas adsorption studies and carbon replication have also served to illustrate that the presence of the regions was not due to electron-beam damage. The presence of extrusions on some samples has been attributed to incomplete loss of monomer on evacuation due to the thickness of the surrounding polymer shell.
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  • 89
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crosslinking of an ethylene-;tetrafluoroethylene copolymer by exposure to an argon plasma, excited by an inductively coupled RF field, is studied over a wide range of pressures and power loadings. The results are interpreted in terms of a two-component, direct and radiative energy-transfer model showing that the outermost monolayer crosslinks rapidly via direct energy transfer from argon ions and metastables.
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  • 90
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2347-2365 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The addition reaction between melamine and formaldehyde has been studied by the direct observation with NMR spectroscopy and high-speed liquid chromatography. All of the nine methylolmelamines, including two isomers of di-, tri- and tetramethylolmelamine could be assigned. The liquid-chromatographic technique was applied to the quantitative analysis of methylolmelamines and the free formaldehyde contents in the reaction mixtures, and the molecular species distributions were determined. By using these quantitative methods, the equilibrium constants and rate constants for the individual reversible reactions were estimated.
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  • 91
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2393-2400 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of tetrafunctional diamines and bifunctional amines with monoepoxy compounds was investigated by gel-permeation chromatography. At a stoichiometrically equivalent ratio of the functional groups or excess of amine, the consecutive reaction of the epoxide groups with the hydrogen atoms of the amino groups is the only reaction that is taking place; if epoxide is present in excess, the OH groups formed in the reaction are gradually added to the epoxide groups. The ratio of the rate constants of the reaction of the epoxy group with the hydrogen atoms of the primary and secondary amino group was calculated from the concentrations of the reaction products at various excess amounts of amines. The ratio is in good accord with the value calculated from the gel points and limiting stoichiometric ratios in the curing of diepoxides with diamines.
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  • 92
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2401-2410 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An organolithium reagent substituted with a primary amine-protecting group [i.e.,—N(TMS)2] has been prepared and used to polymerize 1,3-butadiene and isoprene. A method is described for converting the resulting—N(TMS)2-containing polydienes into—NH2-containing polymers. Both —N(TMS)2- and —NH2-terminated polydienes have been characterized with regard to microstructure, Mn, and Mw/Mn data, as well as qualitative and quantitative end-group analyses. The described preparative procedures represent a convenient route to the elusive primary amine-terminated polydienes.
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  • 93
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2411-2425 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of perfluorocarbons and fluorohydrocarbons was investigated by using both continuous and pulsed rf discharge (100 μsec on and 900 μsec off). Plasma polymerization of perfluorocarbons is generally slower than that of hydrocarbons, which seems to be due to the absence of contribution of fluorine detachment to the plasma polymerization. Presence of multiple bond(s) or cyclic structure in a monomer is necessary to obtain high enough polymerization; however, the plasma polymerization mechanism postulated to plasma polymerization of hydrocarbons is still valid to these monomers. Cyclic structure is very effective to enhance the plasma polymerization capability of perfluorocarbons. Saturated straight-chain perfluorocarbons do not polymerize well in plasma, but the grafting of fluorine-containing functions on the surface of polymeric substrate can be achieved by the plasma of these compounds. The effect of pulse on the plasma polymerization was found to be similar to that found for hydrocarbons.
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  • 94
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2427-2433 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermal decomposition mechanisms of poly(vinyl chloride) (PVC) and the effects of a few metal oxides on the pyrolysis of PVC were previously reported. In the present work, 33 metal oxides were investigated to determine their effects on the thermal decomposition of PVC, by using a pyrolysis gas chromatograph. Most acidic oxides accelerate the recombination of chlorine atoms with double bonds, since PVC containing these metal oxides easily release lower aliphatics, toluene, ethylbenzene, o-xylene, and chlorobenzenes. On the other hand, most basic metal oxides, such as oxides of alkaline earths or silver, inhibit the recombination. These tendencies observed in the thermal decomposition of PVC agree with the contributions of corresponding metal salts to the dehydrochlorination of PVC proposed by other workers. This means that thermal decomposition or dehydrochlorination of PVC is affected by irregularities in head-to-tail linkages formed by the recombination of chlorine atoms during heat treatment of PVC.
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  • 95
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2435-2440 
    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 metal oxides upon the thermal decomposition of poly(vinyl chloride) (PVC) were previously reported. In this work, 23 metal chlorides were investigated to determine their effects on the thermal decomposition of PVC by pyrolysis-gas chromatography at 500°C. Each metal chloride exhibits influences on the course of thermal decomposition of PVC almost similar to the corresponding metal oxide except for a few elements; the metal chlorides from acidic metal oxides accelerate the thermal decomposition of PVC, but the metal chlorides from basic metal oxides do not. On comparing the effects of metal oxides and metal chlorides on the thermal decomposition of PVC, most metal chlorides were found to accelerate the thermal decomposition of PVC more than the corresponding metal oxides, owing to ease of addition of the chlorine atoms released from metal chloride to the dehydrochlorinated chains. It is concluded from these results that the thermal decomposition of PVC containing metal salts is markedly influenced by the ease with which chlorine atoms are released from the corresponding metal chloride.
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  • 96
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2441-2451 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bisbenzils have been prepared by nucleophilic aromatic nitro displacement reactions. These materials, some model compounds, and some polyphenylquinoxaline polymers prepared from them were rigorously analyzed by 13C-NMR spectroscopy. The observed chemical shifts were in excellent agreement with calculated values based on model systems. This served as the strongest evidence to support the proposed structures and gave additional intimate structural information on the polyphenylquinoxalines.
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  • 97
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2469-2477 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interactions of integral-or pendant-type polycations with sodium-1-anilino-8-naphthalene sulfonate (ANS) were studied by means of their fluorescent spectra. The emission maxima shift to the lower wavelength and fluorescent intensities increase greatly as a result of such complexations. This result may be attributed to the electrostatic interaction and the specific nonpolar environment around the bound ANS. The hydrophobic property in the domain formed by a polycation chain depends on the increase of methylene groups or the existence of a xylylene group between two adjacent cationic sites on the main chain, the existence of benzyl groups on the side chains, and the increase of their molecular weights. It is shown that the hydrophobicities in the domains of polyelectrolytes also change with their conformational changes, i.e., the more contracted their conformations are, the stronger their hydrophobicities are.
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  • 98
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2453-2468 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study was made of the mechanism of benzene polymerization by aluminum chloride-cupric chloride. Our main effort was devoted to propagation with the aim of resolving a literature conflict as to whether a cationic or radical pathway is involved. When equimolar mixtures of benzene and haloarene are polymerized, the resulting copolymers are composed almost exclusively of benzene monomer. This approach is based on the known relative reactivities of the monomers toward electrophilic and radical species. The amount of haloaromatic present in the copolymer was determined by elemental analyses and confirmed by infrared spectroscopy. These results are strongly indicative of propagation by an electrophilic moiety. The presence of oxygen in the reaction mixture was found to have no significant effect on the rate or yield of the polymerization, in contrast to a previous published report. The progress of the reaction was followed by titration of the evolved hydrogen chloride. Phenyl radicals, obtained by the thermal decomposition of benzoyl peroxide in benzene, were found to be incapable of initiating the polymerization in the presence of cupric chloride. Increased yields of biphenyl and the presence of chlorobenzene point to oxidation of intermediate radicals by cupric chloride. None of the experimental evidence is satisfactorily interpreted by radical propagation. The data are nicely rationalized on the basis of cationic chain extension, apparently via a radical cation initiator.
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  • 99
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2479-2495 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The copolymerization of cyclohexene and sulfur dioxide to form an alternating copolymer was initiated by tert-butyl hydroperoxide. The enthalpies and entropies of formation of the cyclohexene-sulfur dioxide charge-transfer complex, which is present during the copolymerization, were determined in two solvents by means of ultraviolet spectroscopy. The reduction of ultraviolet absorption during copolymerization afforded a convenient means of investigating reaction kinetics. No evidence of the direct involvement of the complex in polymerization initiation was found. The observation that the use of unpurified cyclohexene led to spontaneous initiation appears to point to adventitiously formed hydroperoxide rather than the charge-transfer complex as providing initiating radicals which are produced by the redox reaction of the hydroperoxide with sulfur dioxide. A competing heterolytic scission reaction was found to result in the formation of tert-butyl peroxide and sulfuric acid. This reaction caused the polymerization reaction to stop after a short period of time due to a time-dependent decrease in initiator concentration.
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  • 100
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    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2497-2509 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cis-transoidal (orange, soluble, and of low crystallinity) and cis-cisoidal (red, insoluble, and highly crystalline) polyphenylacetylenes (PPA) were prepared by Ziegler-Natta catalysts and trans-cisoidal (yellow, soluble, and amorphous) polyphenylacetylenes were prepared by using phosphine complexes, TiCl4 and by thermal initiation. The cis-transoidal and cis-cisoidal structures isomerize thermally in the solid state above 100°C. In solution the cis-transoidal structure isomerizes above 80°C. The polymers obtained by thermal isomerization are soluble, amorphous, and have a trans-cisoidal structure. At temperatures higher than 120°C the cis-trans isomerization is accompanied by cyclization and by scission of the polymer chain. A method was developed for determination of cis content of cis-transoidal and cis-cisoidal polyphenylacetylenes.
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