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  • Physics  (5,199)
  • ASTROPHYSICS  (5,125)
  • 1980-1984  (5,629)
  • 1975-1979  (4,695)
  • 1
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    Mathematical and conceptual foundations of 20th-century physics (1984)
    Amsterdam ; New York : North-Holland Pub. Co
    Details
    Keywords: DDC 530.1 ; LC QC20 ; Mathematical physics ; Physics ; Quantum theory ; Relativity (Physics)
    ISBN: 9780444875853
    URL: http://www.sciencedirect.com/science/publication?issn=03040208&volume=100
    Language: English
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  • 2
    Electronic Resource
    Electronic Resource
    Initiation and propagation steps in the equibinary polymerization of butadiene by bis(h3-allylnickel trifluoroacetate) (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1147-1160 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization of butadiene by bis(h3-allylnickel trifluoroacetate) in benzene and o-dichlorobenzene solvents yields an equibinary 1,4-polybutadiene, containing equal amounts of cis and trans isomers. Initiation proceeds by addition of the allylic moiety of the initiator to a butadiene molecule. The rate of initiation is high enough to ensure complete consumption of the catalyst for a monomer/catalyst molar ratio of about 10 at 5°C. The propagation exhibits the characteristics of a “living” polymerization: the molecular weight is proportional to the conversion, and at the end of the reaction, the average degree of polymerization is equal to the monomer/catalyst molar ratio. Living polybutadienyl-nickel trifluoroacetate is able to reinitiate not only butadiene polymerization but also allene polymerization. However, for high [monomer]/[catalyst] ratios, conversion-dependent transfer reactions limit the molecular weight to 7000 in benzene and to 70,000 in bulk polymerization in the presence of small amounts of o-dichlorobenzene.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.170130511
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  • 3
    Electronic Resource
    Electronic Resource
    Degradation of polymer mixtures. VIII. Blends of poly(vinyl acetate) with poly(methyl methacrylate) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1839-1856 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The degradation of blends of PVA and PMMA in the form of films cast from a common solution of the polymers has been studied by TVA, TG, and EGA (evolved gas analysis) for acetic acid. Volatile degradation products have been characterized by spectroscopic and GLC techniques. Molecular weight, spectral and thermal stability changes in PMMA extracted from partially degraded blends have been examined. These blends behave in a closely analogous manner to PVC-PMMA blends already investigated. The results suggest that the PMMA component of the heterogeneous blends is modified in two ways: (1) in a destabilization reaction series initiated by attack of acetate radicals generated in the PVA phase which migrate into the PMMA phase, and (2) in a stabilization reaction involving conversion of ester side groups to acid and subsequently to anhydride ring structures which act as blocking points for depolymerization. The rate of acetic acid production in the blend is less than in PVA degraded alone. The mechanism of degradation of PVA is reconsidered in the light of these results.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140804
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  • 4
    Electronic Resource
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    Polymerization and copolymerization of trioxane: Factors influencing molecular weight and end groups (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1183-1208 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In bulk polymerization and copolymerization of trioxane with ethylene oxide, it has been shown that p-chlorophenyldiazonium hexafluorophosphate is a superior catalyst as compared to boron trifluoride dibutyl etherate (BF3 · Bu2O). Polymers and copolymers of significantly higher molecular weight have been obtained. The higher molecular weight has been attributed primarily to less inherent chain transfer during propagation, which in turn can be attributed to the superior gegenion PF6-.The polymerization proceeds via a clear period followed by sudden solidification. Faster polymerization and higher molecular weight polymers have been observed for homopolymerization than for copolymerization. The polymer yield obtained after solidification is determined by both rate of polymerization and rate of crystallization of polymers. These rates, in turn, are dependent on the catalyst concentration. The molecular weight is determined both by polymer yield and extent of inherent chain transfer. In the range of monomer to catalyst mole ration [M]/[C] = (0.5-20) × 104 investigated, it has been found that in the higher range, the polymer yield is independent of the catalyst concentration and the extent of inherent chain transfer is inversely proportional to the half power of catalyst concentration: [M]/[C] = (0.5-8) × 104 for homopolymerization and (0.5-3) × 104 for copolymerization with 4.2 mole % ethylene oxide. In the lower range, the yield decreases with catalyst concentration and the extent of inherent chain transfer is inversely proportional to higher power of catalyst concentration. The dependence of molecular weight of polymers on catalyst concentration has been shown to be a complex one. The molecular weight goes through a maximum as the catalyst concentration is decreased. The maximum molecular weights have been obtained at [M]/[C] ≈ 8 × 104 for homopolymerization and ∼3 × 104 for copolymerization with 4.2 mole % ethylene oxide. Prior to reaching maximum the molecular weight is inversely proportional to the half power of catalyst concentration indicating it is primarily controlled by inherent chain transfer. Upon further decrease of catalyst, molecular weight decreases as a result of both a decrease in polymer yield and an increase in inherent chain transfer.In copolymerization of trioxane and ethylene oxide, it has been ascertained that methylene chloride exhibits a favorable solvating effect. Although higher inherent chain transfer takes place in copolymerization than in homopolymerization, the extent of chain transfer is independent of ethylene oxide concentration. The difference in polymer yield and molecular weight a t different ethylene oxide concentrations is attributed primarily to the difference in kp/kt ratio. It also has been demonstrated that end capping of polymer chains can be accomplished by the use of a chain transfer agent - methylal.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.170130514
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  • 5
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    Determination of rate constants for polymerization of styrene initiated by 2,2′-azobisisobutyronitrile by utilizing steady-state population densities (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1241-1251 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A theoretical description of chain-growth polymerization is presented in terms of a distributed parameter model. Analysis of molecular distributions of macromolecular materials results in graphical procedures capable of yielding absolute values for kinetic constants. A steady-state analysis of styrene polymerizations initiated with 2,2′-azobisisobutyronitrile in toluene yielded the following rate information, which is in qualitative agreement with previously published results: f = 0.4; Ki = 1.58 × 1015 exp {-30,800/RT} Ktc/K2p = 1.10 × 10-5 exp {13,200/RT}.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.170130517
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  • 6
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    Polymerization of allyloxyacetaldehyde. Polymerization and tishchenko reaction initiated by triethylaluminum (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1257-1263 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.170130519
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  • 7
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    Molecular weight distribution studies. I. Radiation-induced polymerization of liquid α-methylstyrene (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1271-1284 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The concentration of water in purified and BaO-dried α-methylstyrene was found to be 1.1 × 10-4M. The radiation-induced bulk polymerization of the α-methylstyrene thus prepared was studied in the temperature range of -20°C to 35°C. The polymerization rate varied as the 0.55 power of the dose rate. The theoretical molecular weights and molecular weight distribution were calculated from a proposed kinetic scheme and these values were then compared with those found experimentally. The agreement between these two was reasonably close, and therefore it was concluded that, from the molecular weight distribution point of view, the proposed kinetic scheme for the cationic polymerization of α-methylstyrene is an acceptable one. The rate constant for chain transfer to monomer kf changed with temperature and was found to be responsible for the decrease in the molecular weight of the polymer with increase in temperature. kf and kp at 20°C were found to be 0.95 × 104 l./mole-sec and 0.99 × 106 l./mole-sec, respectively.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.170130601
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  • 8
    Electronic Resource
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    Estimation of molecular weight distribution based on chain length dependence of termination rate (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1297-1307 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: When a chain length dependence of polymer-polymer termination is given by kt,ns = const. (n-2a + s-2a) where n and s are the chain lengths for the polymer radicals and a is parameter, an instantaneous weight fraction of the non-reacting polymers is derived as: \documentclass{article}\pagestyle{empty}\begin{document}$$ g(n) = \frac{{n^{2 - 2a} \exp \left\{ { - [phn^{1 - 2a} /(1 - 2a)] - h\bar kn} \right\}}}{{p_n \int_1^\infty {n^{1 - 2a} \exp \left\{ { - [phn^{1 - 2a} /(1 - 2a)] - h\bar kn} \right\}dn} }} $$\end{document} where h and k̄ are the kinetic parameters, p is a parameter depending on a, and pn is instantaneous number-average chain length. Such a weight fraction corresponds to the experimental one over a wide range of conversion in the polymerization of styrene. On the scope of this correspondence, the polymer-polymer termination rate is estimated as: k̄t = 8πR0D1/100 ( = 4πRsDs) where R0 is reaction radius between monomer radicals and D1 is the diffusion coefficient of the monomer; Rs is reaction radius between segment radicals with n ≅ 100 and Ds is the diffusion coefficient of the segment. The Fujita-Doolittle theory applies to such a rate. Further, the rate also yields 1.5 × 1071./mole-sec, which is the observable extent at conversions less than 0.2.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.170130603
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  • 9
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    Study on radiation-induced polymerization of vinyl monomers adsorbed on inorganic substances. II. Radiation-induced polymerization of methyl methacrylate adsorbed on several inorganic substances (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1325-1338 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radiation-induced polymerization of methyl methacrylate (MMA) absorbed on such inorganic substances as silica gel, white carbon, silicic acid anhydride, zeolite, and activated alumina was carried out to compare with the case of styrene. The rate of radiation-induced polymerization adsorbed on inorganic substances was high compared with that of radiation-induced bulk state polymerization, as was the case with styrene. Inorganic substrates which contain aluminum as a component element are more likely to be grafted than those which consist of SiO2 alone, as with styrene. The molecular weight distribution of unextractable polymer and extractable polymer differs, depending on the type of inorganic substance. Experiments by a preirradiation method were carried out in case of silica gel, white carbon, and silicic acid anhydride. GPC spectra of the polymer obtained were different from those of polymer formed by the simultaneous irradiation method. It appears that all the unextractable polymer is grafted to the inorganic surface with chemical bond.
    Additional Material: 20 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.170130605
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  • 10
    Electronic Resource
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    Photopolymerization of vinyl fluoride (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1339-1346 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photopolymerization of vinyl fluoride, in the presence of peroxide, was studied in dimethyl sulfoxide (DMSO) solution and in bulk. It was found that high rates of reaction could be obtained in spite of the fact that the polymer precipitates at an early stage. By continuous supply of monomer the precipitated polymer was converted into a transparent bulk polymer.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.170130606
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  • 11
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    Singlet oxygen and polymer photooxidations. II. Photodegradation of an olefinically unsaturated polymer (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 993-1014 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method based on infrared spectral changes in thin films was devised and used to evaluate the relative effectiveness of various types of additives on photodegradative processes in an olefinically unsaturated polymer. Nickel chelates of the thiobisphenol-amine complex type are shown to be quantitatively more effective in retarding the photodegradation of these polymers than other additives having greater singlet oxygen quenching efficiencies, ultraviolet absorption, or radical antioxidant properties. Photosensitization with a singlet oxygen sensitizer (fluoranthene) rapidly produces degradative effects in the polymer which are identical with those of its direct degradation by light. The sensitized effects are also retarded by the nickel chelates. Photosensitization by a hydrogen atom-abstracting sensitizer (a benzophenone) proved considerably less effective. The effectiveness of the nickel complexes appears to be due to a combination of their ability to quench singlet oxygen and precusor excited states and their relative stability under photoexposure conditions.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.170130417
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  • 12
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    Self-crosslinkable polymers. I. Copolymerization of glycidyl methacrylate with 2-vinylpyridine and 2-vinyl-5-ethylpyridine (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1017-1028 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A soluble and self-crosslinkable linear copolymer with pendant epoxy and pyridyl groups was obtained from glycidyl methacrylate (M1) and 2-vinylpyridine (M2) or 2-vinyl-5-ethylpyridine (M2) by the action of azobisisobutyronitrile. The monomer reactivity ratios were determined in tetrahydrofuran at 60°C: r1 = 0.510, r2 = 0.620 with 2-vinylpyridine and r1 = 0.57, r2 = 0.62 with 2-vinyl-5-ethylpyridine. These were consistent with the calculated values with the reported Q and e values for these monomers. The intrinsic viscosities of the copolymers with 2-vinylpyridine and with 2-vinyl-5-ethylpyridine were found to be 0.17-0.19 and 0.26-0.38, respectively, in tetrahydrofuran at 30°C; they were independent of the copolymer composition. The copolymers were amorphous, had no clear melting points, and became insoluble crosslinked polymers under heating without further addition of any curing agents.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.170130501
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  • 13
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    Aromatic polyethers, polysulfones, and polyketones as laminating resins. V. Polymers containing acetylenic side groups (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1095-1106 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,3-Bis(p-phenoxybenzenesulfonyl)benzene and 4,4′-diphenoxydiphenyl sulfone were polymerized with isophthaloyl and terephthaloyl chloride in Friedel-Crafts type polymerizations. These polymers had 2,4-diphenoxyacetophenone in the backbone. The acetyl group was then converted into an acetylene group. They were crosslinked effectively by cyclization of the acetylene groups with a catalyst or by cyclo-addition with bisnitrile oxides.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.170130506
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  • 14
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    Effect of pH on the reactivity ratios in aqueous solution copolymerization of acrylic acid and N-vinylpyrrolidone (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1987-1992 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acrylic acid (AA) and N-vinylpyrrolidone (NVP) were copolymerized in aqueous solution at 30°C in the pH range 4-9 and the monomer reactivity ratios (r1 for AA and r2 for NVP) were determined as a function of pH from the high conversion data by using both the differential (YBR) and the integrated copolymerization equations. The value of r1 decreased from 5.2 at pH 4 to a minimum of 1.3 at pH 5 and then increased to 8.1, 6.6, and 7.2 at pH 7, 8, and 9, respectively. Addition of 1M NaCl at pH 6.5 restored the r1 nearly to that at pH 4, the predominantly un-ionized acid. The r2 values for NVP were nearly zero at all pH values except at pH 5. The variation of the reactivity ratios with pH was examined in terms of the electrostatic interactions between the ionized monomer molecules, the rate of homopolymerization of acrylic acid, and the cation binding to the poly(acrylic acid) molecules. The r2 values for NVP compared favorably with the literature values reported in bulk and organic solvent systems, although r1 values are much higher.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140815
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  • 15
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    Polymerization of coordinated monomers. XII. Alternating copolymerization of γ-crotonolactone with styrene with the use of stannic chloride (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1993-2007 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: γ-Crotonolactone and styrene copolymerize alternately in the presence of stannic chloride at -10°C under photoirradiation. The intrinsic viscosity of the resulting copolymer is in the range of 0.6-0.8 dl/g at 30°C in chloroform. The equilibrium constants for the complex formation between stannic chloride and γ-crotonolactone were determined in 1,2-dichloroethane-toluene solution at 0 and -20°C by use of absorption band at 350 nm. Continuous variation plots based on the 1H-chemical shift show a 1:1 interaction between styrene and the γ-crotonolactone coordinated to stannic chloride. The equilibrium constants for the ternary molecular complex formation between the coordinated γ-crotonolactone and styrene were determined in 1,2-dichloroethane in the temperature range from -20 to 0°C. The equilibrium constants, derived independently from the measurements of the nonequivalent protons in γ-crotonolactone, are equal to each other within the experimental error. The mechanism of the alternating copolymerization of γ-crotonolactone and styrene in the presence of stannic chloride is discussed in terms of the homopolymerization of the ternary molecular complex.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140816
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  • 16
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    Oligomeric polyaromatic ether-ketone-sulfones with acetylenic end groups. IX. (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2033-2042 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two oligomeric polyaryl ether-ketone-sulfones with acetylenic end groups have been prepared. These materials which are low melting and readily soluble in organic solvents on heating undergo reactions which are presumably trimerizations of the terminal acetylenic groups to give cured polymers which do not soften until about 200°C and which are stable in circulating air at 300°C with less than 10% weight loss in 10 days.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140819
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  • 17
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    Polymerization of coordinated monomers. XIII. Binding in the ternary molecular complex composed of γ-crotonolactone, styrene, and stannic chloride (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2009-2022 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The time-averaged orientation of the styrene molecule in the ternary molecular complex composed of stannic chloride, γ-crotonolactone, and styrene is determined by use of 1H-chemical shifts of the nonequivalent protons of the γ-crotonolactone. The chemical shift change for each of the various protons of the γ-crotonolactone on the ternary molecular complex formation can be represented by the anisotropic shielding effect of the benzene ring of one oriented styrene molecule. This fact indicates that the ternary molecular complex has a definite time-averaged conformation, though the “complexing” styrene molecule exchanges between in the oriented state and in the free state more rapidly than the time scale of the 1H-NMR spectrometry. The magnitudes of the Coulomb, induction, dispersion, charge-transfer, and exchange-repulsion energies between the γ-crotonolactone and the styrene in the ternary molecular complex are estimated by use of the result of the extended Hückel calculation and that of absorption spectrometry. The Coulomb and dispersion forces between the carboryl group of the coordinated γ-crotonolactone and the benzene ring of the styrene function mainly in the ternary molecular complex formation. Both the induction force and the charge-transfer force make a small contribution to the ternary molecular complex formation.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140817
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  • 18
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    Conductance studies of salt solutions in the presence of poly(vinylbenzo crown ethers) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2023-2031 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conductance of acetone and methyl ethyl ketone solutions of tetraphenylborate salts in the presence of homopolymers and styrene copolymers of vinylbenzo-15-crown-5 and vinylbenzo-18-crown-6 was studied, and the results compared with data obtained for crown ethers. Polycations are formed on binding cations to the poly(crown ethers), and the conductance behavior of the polyelectrolytes depends on the nature of the cation-crown complex and the spacing between crown moieties which in turn determines the charge density on the polymer chain. The compositions of the crown-cation complexes were determined for crown ethers. The complex formation constants of sodium and potassium cations to poly(vinylbenzo-18-crown-6) were found to change as more cations bind to the chain. This is not the case for the copolymers where the crown ligands are spaced farther apart. A mixture of poly(vinylbenzo-15-crown-5) and 10-3M potassium tetraphenylborate in methyl ethyl ketone or acetone has a minimum conductance at a crown to cation ratio of 3.0, but the conductance rapidly increases on addition of crown ether. This was used to qualitatively determine the binding efficiency of a series of crown ethers since the rate of increase in the conductance is a measure of the binding ability of the crown ether to the cation.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140818
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  • 19
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    Liquid crystal polymers. I. Preparation and properties of p-hydroxybenzoic acid copolyestersPaper presented in part at the Society of the Plastics Industry Annual Technical Conference, Washington, D.C., February 4-8, 1975. (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2043-2058 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High molecular weight copolyesters were prepared by the acidolysis of poly(ethylene terephthalate) with p-acetoxybenzoic acid and polycondensation through the acetate and carboxyl groups. The mechanical properties of the injection-molded copolyesters containing 40-90 mole-% p-hydroxybenzoic acid (PHB) were highly anisotropic and dependent upon the PHB content, polyester molecular weight, injection-molding temperature, and specimen thickness. As the injection-molding temperature increased and the specimen thickness decreased, the tensile strength, stiffness, and Izod impact strength increased when measured along the direction of flow of the polymer melt, and the coefficient of thermal expansion was zero. In some compositions these properties were superior to those of commercial glass fiber reinforced polyesters. Maximum tensile strengths, flexural moduli, notched Izod impact strengths, and minimum melt viscosities were obtained with polyesters containing 60-70 mole-% PHB. Higher oxygen indicies (39-40) and heat deflection temperatures (150-220°C) were obtained with 80-90 mole-% PHB.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140820
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  • 20
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    Dependence of structure of dehydrated PVA on the crystallinity of the original PVA (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1223-1240 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(vinyl alcohol) (PVA) films having different crystallinities were prepared by elongating PVA films to different degrees and heating the films with and without elongation treatment at several temperatures between 60 and 200°C. Then, they were dehydrated by heating from 80°C to 230 or 330°C in hydrogen chloride gas. Infrared spectral measurements were made on the dehydrated PVA films obtained. Absorbances of the absorption bands due to several groups seen in the infrared spectra depended only on the density of original PVA films, regardless of its degree of elongation. From these dependences, it was found that the dehydration reaction progressed more easily in the crystalline region than in the amorphous region, that the aromatic rings with four or five adjacent hydrogen atoms were formed mainly in the amorphous region and those with two adjacent hydrogen atoms in the crystalline region, and that the aromatic rings with two isolated hydrogen atoms were formed in both the amorphous and crystalline regions. Relative concentrations of the groups of which the dehydrated PVA were composed were estimated. Comparison of the numbers of carbon atoms among the composing groups indicated that the main groups were the methylene group and the aromatic ring.
    Additional Material: 11 Ill.
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    Monomer-isomerization polymerization. XI. Monomer-isomerization copolymerizations of 2-butene with 2-pentene and 2-hexene with Ziegler-Natta catalyst (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1589-1599 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Pentene and 2-hexene were found to undergo monomer-isomerization copolymerizations with 2-butene by Al(C2H5)3-VCl3 and Al(C2H5)3-TiCl3 catalysts in the presence of nickel dimethylglyoxime or transition metal acetylacetonates to yield copolymers consisting of the respective 1-olefin units. For comparison, the copolymerizations of 1-pentene with 1-butene and 1-hexene with 1-butene by Al(C2H5)3-VCl3 catalyst were also attempted. The compositions of the copolymers obtained from these copolymerizations were determined by using the calibration curves between the compositions of the respective homopolymer mixtures and the values of D766/D1380 in the infrared spectra. The monomer reactivity ratios for the monomer-isomerization copolymerizations of 2-butene (M1) with 2-pentene and 2-hexene, in which the concentrations of both 1-olefins calculated from the observed isomer distribution were used as those in the monomer feed mixture, and for the ordinary copolymerizations of 1-butene (M1) with 1-pentene and 1-hexene by Al(C2H5)3-VCl3 catalyst were determined as follows: 2-butene (M1)/2-pentene (M2): r1 = 0.14, r2 = 0.99; 1-butene (M1)/1-pentene (M2): r1 = 0.30, r2 = 0.74; 2-butene (M1)/2-hexene (M2): r1 = 0.11, r2 = 0.62; 1-butene (M1)/1-hexene (M2): r1 = 0.13, r2 = 0.90.
    Additional Material: 4 Ill.
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    Ethylene polymerization studies with supported cyclopentadienyl, arene, and allyl chromium catalysts (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1607-1617 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Highly active catalysts for low pressure ethylene polymerization are formed when chromocene, bis (benzene)- or bis (cumene)-chromium or tris- or bis (allyl)-chromium compounds are deposited on high surface area silica-alumina or silica supports. Each catalyst type shows its own unique behavior in preparation, polymerization, activity, isomerization, and response to hydrogen as a chain transfer agent. The arene chromium compounds require an acidic support (silicaalumina) or thermal aging with silica to form a highly active catalyst. At 90°C polymerization temperature arene chromium catalysts produced high molecular weight polyethylene and showed, in contrast to supported chromocene catalysts, a much lower response to hydrogen as a chain transfer agent. An increase in polymerization temperature caused a significant decrease in polymer molecular weight. Addition of cyclopentadiene to supported bis (cumene)-chromium catalyst led to a new catalyst which showed a chain transfer response to hydrogen typical of a supported chromocene catalyst. Polymerization activity with tris- or bis (allyl)-chromium appears to depend on the divalent chromium content in the catalyst. Changes in the silica dehydration temperature of supported allyl chromium catalyst have a significant effect on the resulting polymer molecular weight. High molecular weight polymers were formed with catalysts that were prepared using silica dehydration temperatures below about 400°C. Dimers, trimers, and oligomers of ethylene were usually formed with catalysts that were prepared on silica dehydrated much above 400°C. The order of activity of the different types of catalysts was chromocene/silica 〉 chromocene/silica-alumina 〉 bis (arene)-chromium/silica-alumina ≃ allyl chromium/silica.
    Additional Material: 4 Tab.
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  • 23
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    Radiation induced copolymerization of chlorotrifluoro ethylene with butenes (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1645-1656 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radiation induced copolymerization of chlorotrifluoro ethylene (CTFE) with various butenes was studied at temperatures between -20°C and +40°C using 60Co-γ rays.In the case of isobutene (IB) an almost alternating crystalline copolymer is formed in a heterogeneous reaction. At high IB-concentrations a cationic homopolymerization of this olefin occurs simultaneously to the radical copolymerization. The copolymerization rate increases with increasing temperature and degree of conversion. The highest rates are obtained for monomer mixtures with about 80 to 90 mole % CTFE. The decrease in rate for monomer mixtures with still higher CTFE concentrations is assumed to be partly due to the low IB-concentration and partly to degradative chain transfer by the isobutene. In support of this assumption molecular weights and melting points of the copolymer have been determined.Similar results were obtained for butene-1 but in this case, no cationic homopolymerization was observed and the reaction proceeded homogeneously.Cis- and trans-butene-2 only acted as polymerization inhibitors.
    Additional Material: 12 Ill.
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    Kinetics of two-phase bulk polymerization. II. The influence of dissolved polymer (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2121-2134 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of dissolved polybutadiene on the initial rate of polymerization of styrene was investigated by using high-precision dilatometric techniques. The dissolved polymer reduced the rate of polymerization by amounts greater than can be accounted for by a reduction in monomer concentration. Rate reductions increased with the amount of dissolved polybutadiene and with its molecular weight and were greater for benzoyl peroxide initiator than for equal concentrations of azobisisobutyronitrile. Surprisingly, analogous rate reductions were observed when polystyrene were substituted for the polybutadienes, except that at high polystyrene concentrations, the expected autoacceleration was observed. These rate reductions showed no correlation with the viscosity of the reaction mass, nor did the dissolved polymer affect initiator efficiency. At a given level of a particular dissolved polybutadiene, rate reductions were diminished by increasing levels of each initiator, and by adding a chain-transfer agent. Good quantitative agreement was obtained with the number-average length of the growing polymer chains, whether varied by using different initiators, changing initiator level, or adding chain-transfer agent. These results are inconsistent with a chemical mechanism, but they are explained by a proposal originated by North and Reed whereby the dissolved polymer makes the reaction mass a “poorer” solvent for the growing polymer chains, reducing their overall coil dimensions and enhancing their rate of diffusion together for termination.
    Additional Material: 10 Ill.
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    Electronic Resource
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    Acidic dehydration as an analytical method for evaluating ethylene oxide-propylene oxide copolymers (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2135-2145 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acidic dehydration by p-toluenesulfonic acid at 250°C converts poly(alkylene oxides) into dioxane derivatives which can be separated by gas-liquid chromatography. This procedure has been developed as an analytical technique for characterizing some aspects of the molecular structure of polymers of ethylene and propylene oxides. Experimental data on homopolymers, their blends, and some model copolymers have shown that the method is capable of distinguishing between copolymers of different structures, giving correct overall comonomer contents and also ranking copolymers according to their degrees of blockiness.
    Additional Material: 7 Ill.
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    Studies on reactions of the N-phosphonium salts of pyridines. XIV. Wholly aromatic polyamides by the direct polycondensation reaction by using phosphites in the presence of metal salts (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1373-1380 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly-p-benzamide of high molecular weight (ηinh = ∼ in H2SO4) was obtained by the direct polycondensation reaction of p-aminobenzoic acid (p-ABA) by means of diphenyl and triaryl phosphites in N-methylpyrrolidone (NMP)-pyridine solution containing lithium and calcium chlorides. Molecular weight of polymer varied with the amount of these salts, showing maximum values at the concentration of about 4 wt-% of LiCl or about 8 wt-% of CaCl2 in the reaction mixture. The reaction temperature at around 80°C gave a polymer of the highest viscosity. The polycondensation reaction was also affected by monomer concentration, solvents, and tertiary amines like pyridine. Similarly, aromatic polyamides with high molecular weight (ηinh values up to 1.34 in H2SO4) were prepared from isophthalic acid and aromatic diamines, whereas terephthalic acid gave only low-viscosity polymers.
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    Gel-permeation chromatography: A procedure that corrects for imperfect resolution (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1401-1416 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Gel-permeation chromatography is an excellent tool for obtaining polymer fractionation data. Inasmuch as chromatograms are functions of instrument operating conditions, an interpretation procedure must be employed to yield correct molecular distributions of macromolecular materials. A procedure is described that corrects for imperfect resolution. Extensive experimental testing of polymeric materials with kinetically known molecular distributions demonstrates its validity in regions where poor resolution is experienced.Applications will allow one to utilize equipment with inherently poor resolution or to operate instruments with high resolution in regions of poor resolution (e.g., rapid analysis).
    Additional Material: 8 Ill.
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    Influence of six- and eight-membered rings on the dynamical behavior of polymers (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1417-1425 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dynamic-mechanical properties of mixtures of polymers with low molecular weight substances containing six- and eight-membered rings were studied. Secondary relaxations have been found and interpreted by means of the theory of conformational motions. There is good agreement of the results with literature data.
    Additional Material: 3 Ill.
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  • 29
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    Starch xanthate-polyethylenimine reaction mechanisms (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1441-1456 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chemical nature of starch xanthate (SX)-polyethylenimine (PEI) reaction products has been studied because of their effectiveness as wet-end additives for improving strength properties of paper. Model compounds, in conjunction with ultraviolet, infrared, and chemical analyses, served to elucidate SX-PEI reaction mechanisms. Aqueous solutions of SX (degrees of substitution 0.1-0.5) were titrated with PEI at pH 5-7 (25-30°C) to form SX-PEI flocculent precipitates that were determined to be polyelectrolyte complexes. However, when solutions of SX-PEI were kept at pH 10-12, products were formed that included dithiocarbamic acid salts in major quantities, PEI thioureas, and minor quantities of O-starch PEI thinocarbamate. Acid precipitation of these SX-PEI polymeric reaction products from their alkaline solutions, which contained residual xanthate and PEI, also yielded polyelectrolyte complexes. Model systems suggest that PEI thiuram disulfide and starch xanthide, possible products of air oxidation, could be present in minor amounts and would react rapidly with PEI to yield thioureas and thioncarbamates, respectively. Apparently, mixtures of xanthate and amine gave (1) dithiocarbamic acid salts from both xanthate groups and CS2 (decomposition from xanthate), (2) thioureas from both dithiocarbamic acid salts and thiuram disulfide, and (3) thioncarbamates, principally from xanthate as opposed to xanthide.
    Additional Material: 7 Ill.
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    Polymerization of α-amino acid N-carboxy anhydrides initiated by histamine in N,N-dimethylformamide (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1747-1756 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of α-amino acid N-carboxy anhydrides (NCAs) initiated by 4-aminoethylimidazole (histamine) was studied in order to synthesize poly(amino acids) containing an imidazole nucleus at the end of polymer chain. On the basis of the kinetical measurements, it was found that the rate of polymerization is proportional to the first order in both NCA and initiator concentrations and that the initiation reaction is predominantly caused by the primary amine with the highest basicity in a histamine molecule. Binding of the histamine fragment to the end of polymer chain was confirmed by elementary analysis, nuclear magnetic resonance spectroscopy, and measuring the number-average molecular weight of the resulting polymers. It was thus possible to prepare poly(amino acids) with a pendant histamine. In addition, the lowering of the number-average degree of polymerization of the polymers prepared was observed under the condition that the initial molar ratio of NCA to histamine was larger. It was caused by the reinitiation of polymerization by the imidazole nucleus at the chain end.
    Additional Material: 6 Ill.
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    Block and graft copolymers by selective cationic initiation. III. Synthesis and characterization of bigraft copolymers (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1765-1781 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and characterization of new bigraft copolymers poly[(ethylene-co-propylene-co-1,4-hexadiene)-g-styrene-g-α-methylstyrene] (Nordel-g-PSt-g-PαMeSt) and poly[(ethylene-co-propylene-co-1,4-hexadiene)-g-isobutylene] (Nordel-g-PSt-g-PIB) are described. The synthesis involves the use of a polyhydrocarbon backbone containing allylic chlorines and bromines (chlorobrominated Nordel) in conjunction with a suitable alkylaluminum compound to initiate selectively the polymerization of a monomer (generally styrene) from the chloride sites and subsequently to initiate the polymerization of another monomer (α-methylstyrene or isobutylene) from the bromide sites. Conditions conductive to selective and sequential initiation have been worked out. The pure bigrafts are obtained by selective solvent extraction and their homogeneity (by gel permeation chromatography), overall composition (by nuclear magnetic resonance spectroscopy) and molecular weight (by osmometry) are determined.
    Additional Material: 4 Ill.
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    Study of radiation-induced polymerization of vinyl monomers adsorbed on inorganic substances. IX. Preirradiation polymerization of styrene-silica gel system (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2193-2205 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Preirradiation polymerization of the styrene-silica gel system was studied in detail. Both graft polymers and homopolymers have bimodal GPC spectra. High molecular weight peaks were formed in a radical mechanism and the low molecular weight peaks were formed in a cationic mechanism as same as those in the simultaneous irradiation polymerization. The rate of formation of the low molecular weight peaks was very high compared with that of the high molecular weight peaks. Monomer conversion and percent grafting leveled off at about 1-2 Mrad. Radiation dose dependence of the four peaks were different from each other. Monomer conversion and percent grafting decreased as the preheating temperature of silica gel increased. The amount of the low molecular weight peaks of graft polymers depended on the number of silanol groups, as in the case of the simultaneous irradiation polymerization. A reaction mechanism for the preirradiation polymerization is proposed based on the results obtained.
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    Polyimidothioether-polysulfide block polymers (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1819-1842 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of a new class of block polymers that contain alternating polyimidothioether “hard” blocks and polysulfide elastomer “soft” blocks is described. Compositions with 70% and greater polysulfide component are solvent-resistant, thermoplastic elastomers exhibiting room temperature tensile strengths of up to 1500 psi and ultimate elongations of nearly 800%. The physical properties are a strong function of test temperature due to relatively short polyimidothioether blocks, 850 ≤ M̄n ≤ 3500 g/mole. These short polyimidothioether blocks were necessary to minimize degradation of the polysulfide elastomer blocks during thermal processing at temperatures ∼100°C above the “hard” block domain Tg.
    Additional Material: 15 Ill.
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    Poly(alkyl α-chloroacrylates). IV. Tacticity analysis from 300 MHz proton magnetic resonance spectraFor preceding papers see Wesslen et al.1-3 (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1803-1818 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 300 MHz proton magnetic resonance spectroscopy was applied to the determination of triad structures of three poly(alkyl α-chloroacrylates) of widely varying stereoregularities. Assignments and quantitative analyses were made for all of the tetrad peaks in the backbone methylene resonance of poly(methyl α-chloroacrylate), poly(ethyl α-chloroacrylate), and poly(isopropyl α-chloroacrylate). In addition the methyl singlet peaks of poly(methyl α-chloroacrylate), the methyl triplet peaks of poly(ethyl α-chloroacrylate) which had not been amenable previously to resolution at 220 MHz, and the methyl doublet peaks of poly(isopropyl α-chloroacrylate) were resolved, and the triad values which were obtained from these pendant ester group resonances compared favorably with triad values calculated from experimental tetrad values. As a demonstration of the internal agreement of the triad and tetrad peaks assignments, statistical calculations of the stereochemical structures of the actic and syndiotactic polymers were generally described well or to a first approximation by random selection statistics (Bernoullian) while the stereochemical statistics of the moderately to highly isotactic polymers were consistent with a nonrandom statistical process (first-order Markovian), as expected.
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    Reaction of poly(vinyl alcohol) with pentavalent vanadium ion (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2251-2261 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of poly(vinyl alcohol) (PVAL) with V(V), i.e., pentavalent vanadium ion, was studied in aqueous H2SO4 medium. The viscosity change of reaction mixture with time showed a peculiar feature owing to formation of labile complex between V(V) and PVAL and the subsequent decomposition of the complex. On the other hand, the change of viscosity disappeared when NaOH was added during the reaction to neutralize H2SO4 in the reaction mixture. Under a suitable condition, the reaction mixture set to a gel as a result of complex formation. It appeared that reactive sites in PVAL responsive to complexing with V(V) were 1,2-glycol unit and 1,2-ketoalcohol unit resulting from the oxidation of 1,2-glycol by V(V). The rate of oxidation was increased with increasing H2SO4 concentration. The main-chain scission of PVAL took place to an insignificant extent, unless the reaction condition was severe. Based on the results obtained a reaction mechanism has been proposed.
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    Chromatographic techniques for rapid measurement of gel in elastomers (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1575-1587 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Techniques for measuring gel contents of elastomers by liquid exclusion chromatography are described. Chromatographic methods are based on solubilizing aqueous latex in a water-miscible elastomer solvent. The resulting mixture of solubilized elastomer and dispersed gel particles is separated and analyzed by liquid chromatography, columns packed with porous glass particles and a differential refractometer detector being used. Applicability of these techniques is illustrated with results for typical nitrile elastomers in methyl ethyl ketone. Chromatographically measured gel contents in the range 30-80% gel were in good agreement with those measured by a classical, 3-day static method. Repeatability of chromatographic measurement was ±1.35% gel. The entire analysis, including solution preparation, required less than 1 hr and can be as short as 10-20 min.
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    Monomer-isomerization polymerization. XIII. Monomer-isomerization polymerization of 1,4-cyclohexadiene with Ziegler-Natta catalyst (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1601-1605 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,4-Cyclohexadiene underwent monomer-isomerization polymerization to yield poly(1,3-cyclohexadiene) with a Ziegler-Natta catalyst comprising TiCl4-Al(C2H5)3 catalyst with Al/Ti molar ratios of 0.5-3.0 at 60°C for 96 hr. Good yields of polymer were obtained (49.5% yield at Al/Ti = 3.0; [η] = 0.04 dl/g). The infrared and NMR spectra of the polymer were identical to those of poly-(1,3-cyclohexadiene), confirming that 1,4-cyclohexadiene first isomerizes to 1,3-cyclohexadiene and then homopolymerizes to give poly-1,3-cyclohexadiene. 1,3-Cyclohexadiene polymerized without isomerization easily in the presence of TiCl3-Al(C2H5)3 catalyst at Al/Ti molar ratios of 0.5-3.0 at 60°C for 3 hr (76.3% yield at Al/Ti = 3.0; [η] = 0.06 dl/g).
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    Trityl-initiated copolymerizations of propylene oxide with tetrahydrofuran. VIII. Influence of reaction parameters (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1619-1643 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The copolymerization of propylene oxide (PO) with tetrahydrofuran (THF) in dichloroethane (DCE) has been studied at -10, 0, +10, and +20°C. The reactions were initiated by triphenylmethyl cations associated with the following gegenions: PF6-, SbF6-, and AsF6-. The overall energies of activation (Eα of PO and Ea of THF) obtained with the three gegenions increase as one passes from PF6- to AsF6- then to SbF6-, though the magnitude of the increase in each case is not substantial. On the other hand, the associated frequency factors A show a considerable variation with the gegenion. The bimodal distributions of the molecular weights, obtained by GPC with the copolymer produced from reactions initiated with triphenylmethyl hexafluorophosphate, show that the proportions of the lower molecular weight component (L) decrease as the solvent is changed from DCE to toluene, and this is even more marked when bulk polymerization conditions are adopted. The proportions of the higher molecular weight component (H) however increase, as does its molecular weight. The GPC molecular weight distributions of the copolymers initiated with triphenylmethyl hexafluorophosphate in DCE to which water has been added, show that the molecular weight of component H decreases with increasing concentration of water, while that of component L remains practically unchanged at a value of 308. This corresponds to an average degree of polymerization (DP) of 4 to 5. The NMR and infrared spectra of copolymers prepared in the presence of still higher initial water concentrations indicate that the PO-based polymer segments are present in excess of those required for a 1:1 copolymer.
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    Reaction of diisocyanates with alcohols. I. Uncatalyzed reactions (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1657-1666 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Because diisocyanates are widely used raw materials in the production of urethane elastomers and foams, it is of particular interest, to know the contribution of secondary reactions to the overall reaction between diisocyanates and polyether glycols, because of the well known influence of crosslinks on the physicochemical properties of polyurethanes. A mathematical method is suggested to calculate rate constants for the primary and secondary reactions, the hypothesis being that the allophanate group is the main secondary product. The method has been verified with experimental data obtained by reacting models. In addition, the influence of the [NCO]/[OH] ratio and of temperature on the formation of the allophanate group has been studied. The method has been applied to the reaction of 4,4′-diphenylmethane diisocyanate with poly(oxytetramethylene) glycol, a polyether glycol specifically designed for use in preparing polyurethanes. The results are in complete agreement with the experimental data.
    Additional Material: 6 Ill.
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    Synthesis of polymaleamides by ring-opening polyaddition reaction of N,N′-disubstituted bisisomaleimides with diamines (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1691-1698 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ring-opening polyaddition reaction of N,N′-disubstituted bisisomaleimides with various diamines in N-methyl-2-pyrrolidone at room temperature afforded polymaleamides having inherent viscosity up to 0.7 in almost quantitative yield. These polymers are a new class of homopolymaleamides and ordered alternating copolymaleamides. Almost all of the polyamides were soluble in a wide range of solvents such as dimethylsulfoxide, dimethylacetamide, m-cresol, and formic acid. They did not show any melt temperature, and began to decompose at a temperature ranging between 200 and 300°C.
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    Radiation-induced emulsion copolymerization of tetrafluoroethylene with propylene. VI. Effects of pressure and temperature (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2307-2318 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In a radiation-induced emulsion copolymerization of tetrafluoroethylene with propylene, the effects of pressure and temperature were investigated in the range of 0-40 kg/cm2 and 7-53°C at emulsifier concentration of 0.5 and 2.0%. Both the polymerization rate and the molecular weight of copolymer increase with increasing pressure and decreasing temperature. These facts are mainly due to an increase of the monomer concentration in the polymer particles. The rate of polymer chain formation was found to be independent of pressure and temperature. The initiation reaction is due mainly to the entry of radicals generated in the aqueous phase into the polymer particles. The apparent activation energy is -2.0 to -3.8 kcal/mole for the polymerization in the presence of 0.5% emulsifier, but is nearly zero at an emulsifier concentration of 2.0%. This difference in apparent activation energies at emulsifier concentrations of 0.5 and 2.0% is explained in terms of the termination mechanisms.
    Additional Material: 12 Ill.
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    A note on linear calibration curve for gel-permeation chromatography developed from a single standard (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2321-2321 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140921
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    Polymerization of methyl methacrylate in the presence of graphite (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2327-2328 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/pol.1976.170140923
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    Cure of unsaturated novolacs by addition polymerization (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2323-2325 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Tab.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140922
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    Poly-D-glutamate esters with aromatic side chains: Syntheses by ester interchange reactions and their kinetics (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2329-2334 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140924
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    Polymerization of phenylacetylene by tungsten hexachloride catalysts (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2335-2337 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/pol.1976.170140925
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    Characterization of novolac resins based on p-tert-butylphenol by PMR spectroscopy (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2341-2349 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The direct silylation of tert-butylphenol formaldehyde resins with N,O-bis(trimethylsily)acetamide (BSA) has allowed a more complete analysis of these resins to be made with proton magnetic resonance (PMR) spectrometry. A quantitative determination of mixtures of the monomer, dimer, trimer, and tetramer may be carried out at 100 MHz.
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    Preparation and heat of polymerization of 3-methyl-3-butyl-2-azetidinone (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2357-2363 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of 3-methyl-3-butyl-2-azetidinone, which forms a polymer which is soluble in a number of common solvents including toluene, chloroform, and carbon tetrachloride, is described. Anionic polymerization, carried out in toluene solution in a calorimetric vessel, yielded for the heat of polymerization of a four-membered lactam -19.1 kcal/mole at 25°C.
    Additional Material: 1 Ill.
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    Study of radiation-induced polymerization of vinyl monomers adsorbed on inorganic substances. III. Effect of p-benzoquinone and ammonia on radiation-induced polymerization of styrene adsorbed on silica gel (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2103-2115 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to elucidate the mechanism of radiation-induced polymerization of styrene adsorbed on silica gel, the effect of p-benzoquinone and ammonia was investigated. The high molecular weight GPC peaks of both graft polymers and homopolymers decreased with increasing p-benzoquinone concentration, while the low molecular weight peaks of both graft copolymers and homopolymers decreased with increasing ammonia concentration. The results indicate that the high molecular weight peaks of both graft and homopolymers are formed as a result of a radical mechanism and that the low molecular weight peaks of both types of polymers are formed by a cationic mechanism. In formation of both graft polymers and homopolymers both radical and cationic polymerization take place at the same time.
    Additional Material: 19 Ill.
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    Stereoregulation in the polymerization of methyl α-ethylacrylate by n-BuLi in toluene (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2117-2124 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of methyl α-ethylacrylate was carried out in toluene by n-BuLi at various temperatures. The yield of the polymer decreased with increase in the polymerization temperature and at 30°C and above no polymer was obtained, indicating that the ceiling temperature of this monomer lay between 0 and 30°C. The isotacticity increased with an increase in the polymerization temperature and at 0°C a highly isotactic polymer was obtained. The fractionation of the polymer obtained at -78°C showed that the polymer was a mixture of isotactic and syndiotactic ones. Upon the addition of a small amount of methanol or water in the polymerization mixture the isotacticity of the polymer increased while the yield decreased. Syndiotactic polymer was obtained in the polymerization by n-BuLi in tetrahydrofuran as well as by diisobutyl aluminum diphenylamide in toluene.
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    Polymérisation anionique des diènes. III. Etude thermodynamique de la propagation du butadiène et de i'isoprène par les organo-alcalins (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1855-1867 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The present work is concerned with the influence of the polymerization temperature on the propagation mechanisms of polyisoprenyl- and polybutadienyl-alkali metals. The thermodynamic parameters of the contact ion pairs and free ions propagations have been calculated. With Li+ in dioxane solvent, the vinyl propagation is stereospecific (for isoprene, the propagation is mainly 4-3). In comparison with benzene, the vinyl propagation of the polydienyl-Li contact ions pairs should be due to complexation of Li+ by dioxane, an electron donor having a weak dielectric constant. In general, the stereospecificity of the propagation of contact ion pairs decreases with increasing counterion size; little difference has been observed with K+ and Cs+ ion pairs in dioxane and benzene media. For isoprene, the methyl substituant should have chiefly a steric effect in the propagation of free ions, whereas it should confer a polar character to the isoprene molecule in the presence of ions pairs.
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    Polyene sequence distribution in thermally degraded poly(vinyl chloride) (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1889-1899 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A kinetic model for the formation of polyene sequences during the thermal degradation of poly(vinyl chloride) in nitrogen is proposed. The model includes a propagation step of the “zipper” type and termination by crosslinking. The initiation can occur randomly or at weak links in the polymer chain. The rate of polyene growth increased with increasing polyene sequence length and passed through a flat maximum at n = 7. The average polyene sequence length was almost constant up to about 0.5% conversion, but then slowly decreased with increasing conversion. This was the result of a larger extent of termination reactions (crosslinking) at higher conversions. At 0.2-0.5% conversion an average polyene sequence length of about 6 was observed. The degradation was carried out in nitrogen at 190°C. The experimental results were obtained from ultraviolet-visible spectrophotometric measurements.
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    C. S. Marvel (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2189-2190 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/pol.1975.170131001
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    Synthesis, mechanism, and property aspects of a new class of polyethers: Poly(1,4-dichloro-2,3-epoxybutane)sPaper presented at the symposium in honor of Professor Carl S. Marvel's Eightieth birthday on January 13-14, 1975, at the University of Arizona, Tucson, Arizona. (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2221-2222 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ring-opening polymerization and copolymerization of the cis and trans isomers of 1,4-dichloro-2,3-epoxybutane has let to an interesting 50% Cl. This family of polymers is expected to acquire commercial importance.
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    Synthesis, characterization, and properties of block and bigraft copolymersPaper presented at the symposium in honor of Professor Carl S. Marvel's eightieth birthday on January 13-14, 1975, at the University of Arizona, Tucson, Arizona. (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2213-2220 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The syntheses of poly(styrene-b-isobutylene), poly[(ethylene-co-propylene-co-1,4-hexadiene)-g-styrene-g-α-methylstyrene], and poly[(ethylene-co-propylene-co-1,4-hexadiene)-g-styrene-g-isobutylene] have been accomplished by using the principle of selective sequential initiation. This method makes use of the large differences in initiation rates that exist between labile organic chlorides and bromides when these halides interact with alkylaluminum compounds. Synthesis conditions have been worked out which allow composition control. These new AB blocks and bigrafts exhibit unusual mechanical and solubility properties, some of which will be described. For example, the Nordel-g-PSt-g-PIB bigraft exhibits only one low temperature transition (DSC, Rheovibron), suggesting an intimate aggregation of Nordel and polyisobutylene phases.
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    Synthesis of aromatic polymers containing anthrazoline and isoanthrazoline unitsPaper presented at the symposium honoring Professor Carl S. Marvel's eightieth birthday on January 13-14, 1975, at the University of Arizona, Tucson, Arizona. (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2233-2249 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The condensation of bisketomethylene monomers with either 4,6-dibenzoyl-1,3-phenylenediamine or 2,5-dibenzoyl-1,4-phenylenediamine catalyzed by acid affords high molecular weight polymers containing the anthrazoline and isoanthrazoline units in the polymer main chain. Base is not an effective catalyst for the production of high molecular weight polymer. The phenyl substitution on the anthrazoline and isoanthrazoline units increases the solubility of these polymers over those in which phenyl substitution is absent. The rodlike character of these polymers, which can be altered by positional isomerism in the chain, has an effect on the solution properties.
    Additional Material: 3 Ill.
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    Pyrolysis-gas chromatography of polymers obtained by Friedel-Crafts reactions of poly(vinyl chloride) with aromatic compounds (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2259-2268 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrolysis, in combination with gas-chromatography technique, was used in the determination of the structure and study of the thermal degradation mechanism of the condensation polymers obtained by Friedel-Crafts reactions of poly(vinyl chloride) with benzene, toluene, and naphthalene. The separation of the pyrolysis products was made using a column packed with chromosorb W (80-100 mesh) coated with 15% silicone SE-52. The identification of the pyrolysis products resulted as a consequence of the thermal decomposition of condensation polymers and their semiquantitative estimation led to the final conclusion that the initial normal chlorine substitution in the macromolecular chain of poly(vinyl chloride) is followed by an important intramolecular cyclization reaction yielding 1,3-methyleneindan units.
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    Gamma-ray induced polymerization of styrene in the presence of methanol (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2291-2304 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics and molecular weight distributions (MWD) of the gamma-ray induced polymerization of styrene in methanol were studied at 35°C, at low conversions and over a dose rate range of 2.76 × 103 to 2.74 × 104 rad/hr. The data obtained at low initial methanol content agreed with previously obtained results and the MWD of the polystyrene formed yielded a single unimodal peak with M̄n in the range of 35,000-480,000. However, at high initial methanol content and low dose rates, at least three peaks were clearly discernible over wide molecular weight distributions. The existence of these peaks is related to the kinetic data and the formation of three distinguishable regions in the polymerization system.
    Additional Material: 15 Ill.
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    Effect of nonelectrostatic interactions on the macromolecular behavior of polyelectrolytes. III. Optical rotatory dispersion of PLL in water and aqueous-organic mixtures (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2305-2318 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have investigated the optical rotatory dispersion of a stereo-irregular polyelectrolyte when neutralized with alkaline and N-tetraalkylammonium hydroxides, both in water and aqueousacetone mixtures.The variations of the optical activity properties during the neutralization can be well related to potentiometric and viscosity measurements. They are interpreted by assuming two kinds of solvation of the chiral centers located on the main chain, to which two partial optical rotary dispersions (ORD) of opposite signs are associated. The observed optical activity changes and specifically the discontinuity occurring in the neutralization range where a conformational transition between a compact structure and a more extended one is initiated, are thus accounted for in terms of the corresponding changes in the state of solvation of chains.
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    Maleimide polymers. III. Color reactions and kinetics (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2327-2334 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have shown previously that the free-radical polymerization kinetics of maleimide can be explained by a scheme for retarded polymerization. The steps involve tautomerization of a growing maleimidyl chain to succinimidyl, the retarded addition of maleimide to the latter, and termination solely by resonance-stabilized succinimidyl radicals. Combination termination is preferred, since this yields a very stable N,N′-bisuccinimidyl structure. Other authors also invoke tautomerization to succinimidyl radicals which they believe terminate by disproportionation with growing maleimidyl chains to generate polymer with unsaturated endgroups. Free-radical-initiated polymaleimides are colored in the presence of base. Our measurements of the absorbance of polymaleimides at 387 and 500 nm in the presence of excess strong organic base show there is essentially no dependence on molecular weight. This suggests that the chromophoric groups are intramolecular and that color does not arise from the ionization of allylic protons associated with terminal double bonds. The near-ultraviolet spectra of polymaleimides in slightly acidic media contain absorption bands at about 288, 320, and 360 nm. The structural impurities that account for these bands cannot be terminal unsaturation. We propose that the origin of these bands is pyrrolinone type structures which are formed by a retarded polymerization step through succinimidyl oxygen.
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    The kinetics of styrene emulsion polymerization (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2087-2102 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study has been carried out on the kinetics of persulfate-initiated emulsion polymerization of styrene in the presence of an anionic (oleate) or mixed anionic-nonionic emulsifier. In both cases it appears that Smith-Ewart kinetics are obeyed, i.e., there is a constant-rate period up to 40-50% conversion, during which there is a concomitant constant molecular weight development. The sharp increases in molecular weight with conversion reported by Grancio and Williams appear to be an artifact resulting from the use of an impure emulsifier (Triton X-100), which acts as a chain transfer agent to reduce the molecular weight by approximately an order of magnitude. Hence there does not appear to be any kinetic justification for assuming an inhomogeneous swollen latex particle (“core-shell” morphology), and normal thermodynamic considerations should still apply to this swelling phenomemon.
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    Formation of free radicals in photoirradiated cellulose. V. Effect of temperature (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2363-2374 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ESR spectra of purified and ferric ion-sensitized celluloses irradiated with ultraviolet light in vacuo at 45, 20, -80, and -196°C were recoreded and compared. Generally, several kinds of spectra, viz., singlet, three-line, five-line, and seven-line spectra, were observed. At higher temperatures, only singlet and three-line spectra of stable free-radical species were detected, whereas at lower temperatures such as at -196°C, two doubled spectra of formyl radicals and hydrogen atoms were also detected in addition to cellulose radicals. It is believed that the intricate spectra observed at low temperatures are superimposed upon spectra generated by free radicals which may or may not be stable at high temperatures. During reirradiation at -196°C with an alternative light sources, i.e., λ 〉 2537 Å and λ 〉 3400 Å, of samples which were irradiated at 20°C or at -196°C, phenomena indicative of radical transformation and formation of new radicals or of decay of radicals in terms of ultraviolet bleaching were observed on studying the changes of line-shapes and relative signal intensities of the spectra.
    Additional Material: 7 Ill.
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    Synthesis of polypyrimidoquinazolinetetraones from N,N′-bis(mesyloxy)pyromellitimide and aromatic diamines (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2391-2396 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel class of polypyrimidoquinazolinetetraones was synthesized by the polymerization of N,N′-bis(mesyloxy)pyromellitimide with aromatic diamines in N-methyl-2-pyrrolidone in the presence of triethylamine as an acid acceptor. The polymerization proceeded probably through the formation of ring-opened adducts, followed by elimination and rearrangement yielding polyamide-isocyanates, which in turn were cyclized to give polypyrimidoquinazolinetetraones. These polymers, which were soluble in strong acids, had inherent viscosities in the range of 0.17-0.27. Thermogravimetric analyses indicated that they began to decompose at around 450°C in air.
    Additional Material: 2 Ill.
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    Formation of free radicals in photoirradiated cellulose and related compounds (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2513-2525 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Free-radical formation in various modifications of celluloses, namely, wood cellulose I, II, III, and IV, rayon cellulose, amorphous cellulose, cotton linters, and absorbent cotton, irradiated with ultraviolet light, has been studied by means of ESR spectroscopy at 77°K. Various types of free radicals were generated from these samples. The line shapes and the signal intensities of the ESR spectra depended greatly upon the degree of crystallinity, the lattice type, and the arrangement of molecules in cellulose. The effect of degree of crystallinity and the amount of sensitizer (Fe3+) absorbed revealed that photochemical reactions in cellulose occurred exclusively in the amorphous regions of the polymer. Free radicals formed in these samples behaved distinctively upon a warm-up process. Phenomena of radical migration and formation of new radicals were observed from the sensitized samples of rayon cellulose and amorphous cellulose.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170141016
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    Investigation of structural changes in wool fibers due to annealing (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2535-2544 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Structural changes in wool fibers after annealing, i.e., storage at 45°C and 80% RH, have been investigated by using the method of laser Raman spectroscopy and by measuring birefringence and density of wool. The results show that CH2 groups in wool give parallel Raman dichroism which increases very significantly after annealing. No increase in birefringence and density occurred after annealing. A hypothesis has been put forward which states that for minimum energy considerations in wool fibers the existence of intrahelix crosslinks other than hydrogen bonds is important. It is highly probable that a large number of electrovalent intrahelix crosslinkages exist between the suitable side groups on the main polypeptide chain in the α-helix of annealed wool.
    Additional Material: 6 Ill.
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    Preparation of block copolymers from occluded vinyl acetate macroradicals (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2545-2552 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Stable vinyl acetate macroradicals were produced by polymerization in a nonviscous poor solvent, a viscous good solvent and a viscous poor solvent. These macroradicals were then allowed to react with a second vinyl monomer to produce block copolymers. The formation of block copolymers was monitored for rate and yield data. The block copolymers produced were poly(vinyl acetate-b-methyl methacrylate), poly(vinyl acetate-b-acrylic acid), poly(vinyl acetate-b-vinylpyrrolidone), poly(vinyl acetate-b-acrylonitrile), poly(vinyl acetate-b-styrene), and poly(vinyl acetate-b-methyl acrylate). The block copolymers were characterized by yield, precipitation in selected solvents, pyrolysis gas chromatography, and differential scanning calorimetry.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170141019
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    Copolymerization characteristics of N-(2,4,6-tribromophenyl)maleimide and N-(2,3,4,5,6-pentachlorophenyl)-maleimide with butadiene and styrene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2587-2588 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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    Polymerization of propylene with TiCl3-AlEt2Cl-polymeric electron donor catalyst (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2565-2574 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymeric donors having ether or carbonyl groups were added to the TiCI3-AlEt2CI catalyst system as the third component, and the effects on the polymerization of propylene were investigated in comparison with the effect of the electron donors with low molecular weight. The polymeric donors were effective in making the catalyst more active, but the donors of low molecular weight depressed the catalyst activity. In the case of poly(propylene glycol dimethyl ether) (PPG-DME), PPG-DME with a number of propylene oxide units (n) of more than 6.7 was effective in enhancing the catalyst activity. These effects were considered to be due to the different reactivities between TiCI3 and AlEt2CI-polymeric donor complexes having various chain lengths.
    Additional Material: 7 Ill.
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    Radiation-induced polymerization of sodium allylsulfonate at high pressure (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2575-2585 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Irradiation of sodium allylsulfonate in aqueous solution at high pressure (up to 9000 kg/cm2) gave a deliquescent white powder which is insoluble in organic solvent. The product was addition polymer of allylsulfonate from the high-resolution NMR and infrared spectra. The rate of polymerization was proportional to the third and second powers of monomer concentration in the initial and later stages, respectively. From the high dependence of the rate on monomer concentration, the reaction was deduced to proceed in an associated monomer or micelle. The rate of polymerization was increased by addition of sodium chloride. The G value for monomer consumption was about 104 at high pressure, which suggests that the degradative chain transfer is not important in the polymerization. Overall activation volumes were -7 and -5 ml/mole in the initial and later stages, respectively.
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    220-MHz NMR spectra of acrylic monomer-2-substituted 1,3-diolefin alternating copolymers (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2553-2563 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An investigation by 220-MHz NMR spectroscopy was carried out on the alternating copolymers of acrylic monomer with 2-substituted 1,3-diolefin. The chain structures were determined. The acrylic monomers used were methyl methacrylate (MMA), acrylonitrile (AN), and methacrylonitrile (MAN); isoprene (IP) and chloroprene (CLP) were the 1,3-diolefins. In the MAN-IP alternating copolymer, the 1-position methylene protons of IP showed an AB quartet peak, confirming the α-1 linkage structure. Similarly, in the MMA-CLP and AN-CLP copolymers, the 1-position methylene protons of CLP showed and AB quartet and an ABX pattern, respectively, confirming the α-1 linkage structure in both these cases also. The α-1 linkage structure was also revealed by the decoupling technique in the MAN-CLP alternating copolymer. The AN-IP and MMA-IP alternating copolymers also possess a bond between the α-position of the acrylic monomer and the 1-position of IP. The monomeric units in the alternating copolymers of acrylic monomers with 2-substituted 1,3-diolefins were generally linked at the α-position of acrylic monomer and the 1-position of 1,3-diolefin. On the other hand, in the Diels-Alder adducts of acrylic monomer with 2-substituted 1,3-diolefin, the reaction takes place between the α-position of acrylic monomer and the 4-position of 1,3-diolefin.The regioselectivity of the alternating copolymers and the Diels-Alder adducts is quite compatible with the expectations from molecular orbital theory.
    Additional Material: 4 Ill.
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    Kinetics of bulk polymerization of styrene-acrylonitrile copolymers (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2589-2593 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170141024
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    The nature of active centers of a polymeric catalase analog (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2595-2605 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition of hydrogen peroxide by a polymer complex of Fe3+ and poly(acrylic acid) partially amidated by diethylenetriamine has been studied. The molecular mechanism of catalysis is discussed. The rate constant of the reaction is k = 6.9 × 107 exp {-2.300/RT}. Decomposition of hydrogen peroxide proceeds via activation by the diethylenetriamine which is a cofactor.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170141101
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    Synthesis and radical ring-opening polymerization of spiro o-carbonates (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2525-2530 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Syntheses and radical ring-opening polymerization of spiro o-carbonates(I-IV) were investigated. These polymers were yellow powders and soluble in common organic solvents. The infrared and NMR spectra indicated that the polymers were alternate copolymers of either and carbonate containing double bonds. The polymerization mechanism is discussed.
    Additional Material: 5 Tab.
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    Synthesis of polyarylaminophosphazenes (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2531-2543 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of a series of Polybis(arylamino)phosphazenes is described. The polymers usually were prepared by treatment of polydichlorophosphazene in benzene-tetrahydrofuran with arylamines/triethylamine at reflux for 48-144 hr. The polymers, having viscosities of 0.3-1.4dl/g, are essentially free of active chlorine sites, as shown by elemental analysis and their longterm hydrolytic stability. Thermal analysis revealed glass transition temperatures between 53 and 105°C and decomposition temperatures between 243 and 266°C. Analysis by differential scanning calorimetry revealed no first-order endothermic transitions. For comparison with the arylamino polymers, polydiethylaminophenylaminophosphazene, polybis(benzylamino)phosphazene, and polybis(β-phenethylamino)phosphazene were prepared and are described.
    Additional Material: 1 Ill.
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    Studies on propagating species in cationic polymerization of styrene derivatives by acetyl perchlorate or iodine. II. Salt effect on the relative reactivity in the cationic copolymerization of styrene derivatives with 2-chloroethyl vinyl ether initiated by iodine (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2621-2629 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To determine the effect of the dissociation of propagating species on the relative reactivity of monomers, 2-chloroethyl vinyl ether was copolymerized with p-methoxystyrene or with p-methylstyrene by using iodine in various solvents at 0°C. A common-ion salt (tetra-n-butylammonium iodide or tetra-n-butylammonium triiodide) was added to these copolymerization systems in a polar solvent to depress the dissociation of the propagating species. The addition of a common-ion salt increased the vinyl ether content in the copolymer. The more the dissociation of propagating species was depressed, the more the vinyl ether content in the copolymer increased. This effect of common-ion salt was in agreement with that of decreasing solvent polarity which yielded vinyl ether-rich copolymer as well. Therefore, the change of the monomer reactivity ratio by the solvent polarity, which used to be explained in terms of a selective solvation, must be reconsidered from the viewpoint of varying degrees of the dissociation of propagating species.
    Additional Material: 7 Ill.
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    Synthesis of oligoesters from oxalic acid and glycerol (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2631-2638 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new synthesis for the polycondensation of oxalic acid and glycerol was used. Polycondensation was carried out in the presence of compounds that do not dissolve oxalic acid and glycerol, but form an azeotropic mixture with water below 100°C. Anhydrous oxalic acid and oxalic acid dihydrate was used for the synthesis of oligoesters. The decarboxylation proceeds parallel with polycondensation of oxalic acid and glycerol was investigated. Decarboxylation of carboxyl groups of glycerol monooxalate was found to be accelerated by the arrangement of primary and secondary hydroxyl groups in the glycerol molecule in the 1,2 position.
    Additional Material: 7 Ill.
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    Alternating copolymerization of the styrene-methyl methacrylate system complexed with diethylaluminum chloride (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2639-2647 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate and molecular weight profiles were obtained for the spontaneous alternating copolymerizations conducted with diethylaluminum chloride. The rate formally fitted an expression, R = kp[MMA][Sty], and the rate constant was established by two distinct methods: (1) from the yield versus time data and (2) from initial rate over a range of initial concentrations; it was determined as 5.4 × 10-6 l./mole-sec with Ea = 4.2 kcal/mole. Molecular weights were determined by gel-permeation chromatography. No increase in molecular weight was observed with increased reaction time. Thus living centers or diradicals are not involved in the process. The M̄n shows a steady decrease with increase in monomer-diethylaluminum chloride concentration but the rate is maximum at equimolar monomer concentrations. The data are interpreted on a chain-transfer mechanism and show close agreement to a model in which the excess complexed acceptor monomer is the transfer agent. The chain-transfer constant of 7.1 × 10-4 l./mole-sec is several orders of magnitude greater than for uncomplexed systems.
    Additional Material: 7 Ill.
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    Chloroaromatic ether amines (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2649-2657 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new and useful class of aromatic amines, based on multichlorinated benzenes and polyphenyls, has been developed. The amines are prepared by reacting the alkali metal salt of p-aminophenol with the chloroaromatics under nucleophilic substitution reaction conditions. Oligomeric amines can be obtained by condensing, e.g., the dialkali salt of bisphenol A and the alkali metal salt of p-aminophenol with the chloroaromatics. The products are mixtures of mono-, di-, and triamines, as a result of the complex functionalities of the chloroaromatics employed. Unique features of the amines include: (1) flame-retarding characteristics; (2) markedly reduced amine reactivity (compared with aniline); (3) thermal stability; (4) good solubility in the usual organic solvents.
    Additional Material: 4 Tab.
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    Polycondensation of pyridine-2,6-dicarboxylic acid with some di- and tetraamino compounds (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2659-2664 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyridine-2,6-dicarboxylic acid phenyl ester was condensed with 3,3′-diaminobenzidine and 3,3′,4,4′-tetraaminodiphenyl ether. Polyamides were also synthesized by condensation of the above ester with p-phenylenediamine, benzidine, 4,4′-diaminodiphenyl sulfide and 4,4′-diaminodiphenyl sulfone. These amides had higher inherent viscosities and greater thermal stability than was reported before. Model compounds of imidazoles were prepared by condensation of the same ester with o-phenylenediamine and 2,3-diaminopyridine and of polyamides by condensation with aniline and 2-aminopyridine. In the case of the polyimidazole, the completely closed ring of imidazole did not form. The ultraviolet spectra of model compounds were compared with those of the polymers. The thermogravimetric curves show that the polymers are stable up to more than 400°C under argon atmosphere. All polymers were insoluble in most organic and inorganic solvents. They dissolved only partially in DMSO and DMF. Inherent viscosity was measured for the soluble polymer fraction.
    Additional Material: 3 Tab.
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    Synthesis of polyamides from active 1-benzotriazolyl diesters and diamines under mild conditions (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2665-2673 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of the solvent on the inherent viscosity of polyamides was investigated in the polycondensation of new active 1-benzotriazolyl diesters, such as 1,1′-(adipolydioxy)bisbenzotriazole and 1,1′-(isophthaloyldioxy)bisbenzotriazole, with diamines. The preferred polymerization media were polar aprotic solvents, including N-methyl-2-pyrrolidone and hexamethylphosphoramide. The solution polycondensation at room temperature afforded a series of polyamides having inherent viscosities as high as 1.8 from both aliphatic and aromatic diamines. The 1-benzotriazolyl diesters were more reactive than di(2,4-dinitrophenyl) isophthalate toward diamines. Prior to polymer synthesis, the aminolysis of some active monoesters was carried out as a model compound study.
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    Polymerization of allyl phenyl ether (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2689-2694 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Allyl phenyl ether polymerized rapidly and quantitatively to a resin with a structure similar to a phenolic thermoset in the presence of boron trifluoride etherate at 50°C. The structure and properties of this polyphenol were studied. A reaction mechanism involving rearrangement was discussed.
    Additional Material: 2 Ill.
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    Syntheses and properties of phosphorus-containing copolyamides (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2675-2687 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Caprolactam was copolymerized with 1,5-dioxo-1-methyl-4-azaphosphepane or methylphosphacaprolactam. The molecular weight of the resulting copolymers decreased with increasing concentration of the thermally labile phosphorus moieties. Copolymers based on ≥40% caprolactam were shown to be crystalline by differential scanning calorimetry and x-ray techniques. As the concentration of the phosphorus structures in the copolymers increased, the glass transition and crystallization temperatures increased while the melting temperatures, crystallinities, and thermal stabilities decreased. Melt blends of nylon 6 and polymethylphosphacaprolactam were shown by differential scanning calorimetry, a selective extraction technique, and elemental analysis to contain appreciable amounts of block copolyamides, and no crystalline random structures were detected. The thermal stabilities of the melt blends were similar to those of random copolymers having comparable concentrations of the phosphorus-containing sequences.
    Additional Material: 8 Tab.
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    Vinyl polymerization. CCCXXXIX. Effect of chain length of nylon 3 on the polymerization of methyl methacrylate initiated with the system of nylon 3, copper(II) ion, and water (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2695-2702 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It was found recently that the system of nylon 3, copper(II) ion, and water could initiate a radical polymerization of methyl methacrylate(MMA). In the present paper, the effect of average chain length of the molecules of nylon 3 on the rate of polymerization of MMA was studied. The rate increased with the chain length of nylon 3. This result was explained well by the fact that the shorter nylon 3 forms a complex with copper (II) ion more easily than longer nylon 3. It was assumed that the shorter nylon 3 fills three or four coordination sites of copper(II) ion and loses the ability to initiate the polymerization. The efficiency of grafting of MMA and the degree of polymerization of MMA homopolymer were independent of the chain length of nylon 3.
    Additional Material: 2 Ill.
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    ESR and NMR study of the γ-ray-induced postpolymerization of vinyl monomers adsorbed on zeolite (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2703-2724 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The γ-ray-induced postpolymerization of acrylonitrile and methyl methacrylate adsorbed on Linde zeolite 13X irradiated at 77°K has been studied between 303 and 343°K as a function of the amount of adsorbed monomer and of the irradiation dose. The change in the nature and the concentration of free radical with temperature and duration of the postpolymerization was followed by the ESR method, whereas the formation of polymer was monitored continuously by the decay of the 1H-NMR absorption line of the monomer under high-resolution conditions. It was found that the overall postpolymerization kinetics may be accounted for by assuming an exponential decay of radical propagation and recombination reactions with chain length. The tacticity of the polymer recovered by destroying the matrix in hydrofluoric acid was determined by 13C-NMR. The probability of isotactic addition of AN and MMA is larger than in the radical polymerization in solution owing likely to the association of adsorbed monomer molecules in pairs preforming an isotactic diad.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170141112
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  • 85
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    Synthesis and properties of polycondensation polymers from compounds with asymmetric functional groups (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2741-2749 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of conditions of polycondensation on the structure of polymers formed from monomers with symmetric and asymmetric functional groups by nonequilibrium polycondensation has been studied for the system with acceptor-catalytic polyesterification of β-hydroxyethyl ethers of bisphenols and terephthalic acid chloride in the presence of triethylamine. Polymers with statistical or regular arrangement of diol residues in the chain can be produced in such systems, depending on the way in which starting compounds are introduced in the reactor. A difference in the reactivity of functional groups in an asymmetric monomer is not sufficient to produce polycondensation polymers with a regular structure. Gradual introduction of the symmetric monomer is essential to yield polymers with predominant “head-to-head” (“tail-to-tail”) configurations. Some properties of the resulting polymers have been studied. Polymers with ordered residues of the asymmetric monomers in the macromolecules have higher softening temperatures and an increased tendency for crystallization than the statistic polymers.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.170131209
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  • 86
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    Graft polymerization of vinyl monomers onto cellulose in presence of soda lime glass. I (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2785-2793 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sodium bisulfite-soda lime glass has proved to be a good initiator for polymerization and graft polymerization onto cellulose of some vinyl monomers. A scheme dealing with the mechanism of initiation has been proposed assuming trapping of the bisulfite radical inside the glass frame-work to form a so-called sulfur-impregnated solid. Such a solid has paramagnetic properties and acts on the vinyl monomers and cellulose as any free-radical-producing source thus leading to polymerization and graft polymerization onto cellulose. Other radicals containing sulfur, such as sulfite, sulfate, and persulfate failed to give such property with soda lime glass. With the sodium bisulfite-soda lime glass system the reactivity decreases in the order methyl methacrylate 〉 ethyl acrylate 〉 acrylonitrile which is inconsistent with the arrangement of acceptor monomers with decreasing electron-donating ability. This may reflect interference of the addition reaction which may take place between the monomer and bisulfite and the rate of which may depend on the activation energy of the monomer.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.170131213
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  • 87
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    Graft polymerization of vinyl monomers onto cellulose in presence of soda lime glass. II (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2795-2805 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the sodium bisulfite-soda lime glass initiating system, crude and true grafting yields increased with increasing ratio of methyl methacrylate to cellulose up to a limit; beyond this limiting value, grafting yields decreased due to the increase of the rate of sodium bisulfite-monomer addition over that of polymerization. Limitation was also achieved on increasing the glass to cellulose ratio through increased termination rates by coupling and disproportionation reactions, as the free radicals are increased. In addition, a limiting value was reached with increasing sodium bisulfite concentration; this may be related to the formation of a nonfunctioning disulfite ion at the expense of bisulfite radicals at high concentrations of sodium bisulfite. The temperature plays a role in this initiating system. Maximum rates of conversion and grafting were achieved at the ceiling temperature. Dissociation of the sodium bisulfite, which decreases with temperature, also has an effect.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.170131214
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  • 88
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    Thermal and radiation-induced dehydrochlorination of poly(vinyl chloride). II. Head-to-head structures (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2813-2826 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of dehydrochlorination of 2,3-dichlorobutane and chlorinated polybutadiene which are model compounds of head-to-head poly(vinyl chloride) has been investigated by pyrolysis, thermal, and ultraviolet-induced decomposition. The activation energy of dehydrochlorination for head-to-head poly(vinyl chloride) in nitrogen was 23 kcal/mole at temperatures of 150-190°C, which is slightly smaller than that (29 kcal/mole) for head-to-tail poly(vinyl chloride). The conjugated double bonds were formed by thermal and radiation decomposition of head-to-head poly(vinyl chloride), similar to head-to-tail poly(vinyl chloride). The probability of polyene formation by radiation-induced dehydrochlorination is larger than that by thermal decomposition and is affected by the conformation and the molecular motion of the main chain. This may be due to the alternative mechanism of dehydrochlorination in the thermal and radiation decomposition. The amount of head-to-head linkage of poly(vinyl chloride) samples prepared with various catalysts is dependent on polymerization temperature rather than the kinds of catalyst. Commercial poly(vinyl chloride) has 6-7 head-to-head linkages per 1000 monomeric units.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.170131216
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  • 89
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    Synthesis of polyhydrazides by ring-opening polyaddition reaction of N,N′-biisomaleimide with dihydrazine and dihydrazides (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2735-2740 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ring-opening polyaddition reaction of N,N′-biisomaleimide with a dihydrazine and dihydrazides was carried out in polar aprotic solvents at room temperature to afford a new class of polyhydrazides having inherent viscosities in the range of 0.1-0.5 in nearly quantitative yields. Almost all of the polyhydrazides were soluble in dimethylformamide, dimethyl sulfoxide, and other polar aprotic solvents. They did not show any clear melt temperature and began to decompose at around 200-300°C.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.170131208
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  • 90
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    Thermal degradation of poly-N-vinylcarbazole (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2867-2870 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.170131224
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  • 91
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    Free-radical polymerization of vinylferrocene. I. Kinetics (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2871-2871 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.170131225
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  • 92
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    Solvent effects on the radiation-induced graft polymerization of styrene onto poly(isobutylene oxide) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2773-2783 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The graft polymerization of styrene onto preirradiated poly(isobutylene oxide) (PIBO) with methanol and benzene was studied. The order of grafting yield and of the number-average molecular weight of graft chains decrease in the order; undiluted styrene 〉 styrene-methanol (1:1) solution 〉 styrene-benzene (1:1) solution. A kinetic treatment to calculate rate constants from the rate of grafting and the molecular weight of the graft chain was proposed. The propagation rate constant kp was 0.2-0.3 l./mole-sec and the termination rate constant kt was 1.0-16.0 l./mole-sec. The ratio kp/kt in this heterogeneous system was larger than that in homogeneous system by a factor of about 104-105.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170141116
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  • 93
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    Photochemistry of fiber-forming polymers. II. Ketone-containing poly(ethylene terephthalates) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2791-2796 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(ethylene terephthalate) copolymers were prepared containing minor amounts of comonomers containing backbone and side-chain ketone groups. The photochemistry of these polymers was studied at 313 nm, both in film and fiber form. It was demonstrated that only the comonomer, dimethyl-γ-ketopimelate (DMKP), gave a copolymer with enhanced sensitivity to ultraviolet degradation in air. Since this sensitivity is reduced in a nitrogen atmosphere, it is suggested that the mechanism involves main-chain scission to form two free radicals by the Norrish type I mechanism, and that recombination of these radicals is reduced by reaction with oxygen. The use of copolymers of this type provides a method for the controlled photodegradation of polyester fibers.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170141118
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  • 94
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    Synthesis of polypyridazinophthalazinediones from dibenzoylphthalic acids and aromatic dihydrazines (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2797-2805 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel class of polypyridazinophthalazinediones has been synthesized by the solution cyclopolycondensation in m-cresol of dibenzoylphthalic acids with aromatic dihydrazines such as bis(4-hydrazinophenyl)methane and bis(4-hydrazinophenyl) sulfone. The polyheterocycles derived from 4,6-dibenzoylisophthalic acid, which had inherent viscosities of up to 0.5, were soluble in m-cresol and hot dichloroacetic acid, whereas the polymers from 2,5-dibenzoylterephthalic acid were practically insoluble in organic solvents. Thermogravimetric analyses showed that all the polymers underwent weight losses of 10% at 490-520°C in both air and nitrogen.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170141119
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  • 95
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    Homogeneous polyblend of poly(vinyl chloride) with α-methylstyrene-methacrylonitrile-ethyl acrylate terpolymer (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 123-127 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Blends of poly(vinyl chloride) (PVC) and α-methylstyrene-methacrylonitrile-ethyl acrylate (AMS-MAN-EA) terpolymer have been prepared and properties studied. The polyblends are unusual inasmuch as they are transparent and possess a single glass transition; therefore, they are homogeneous. The single Tg suggests a single-phase system. The polyblends exhibit rarely observed polymer-polymer compatibility.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140112
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  • 96
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    Copolymerization of trioxane with cyclic acetals. Effect of catalyst on polymerization and monomer reactivity (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 143-151 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The copolymerization of trioxane with cyclic acetals, viz., 1,3-dioxolane, m-dioxane, and 4-methyl-m-dioxane, have been investigated. Three types of catalyst have been employed: a metal chelate, MoO2(AcAc)2; a Lewis acid, BF3·Bu2O; and an ion-pair, It has been ascertained that, in agreement with the previous results on copolymerization of trioxane and ethylene oxide,1 both the polymerization kinetics and the monomer reactivity have been found to be influenced by the catalyst employed. In copolymerization with 1,3-dioxolane, both BF3·Bu2O and have been found to give high molecular weight copolymers with high incorporation of 1,3-dioxolane. However, contrary to the results obtained in copolymerization with ethylene oxide, higher rate and yield have been obtained with BF3·Bu2O, making it a superior catalyst. In copolymerization with m-dioxane, has been found to be a superior catalyst to the others yielding high molecular weight copolymers with high incorporation of m-dioxane. In copolymerization with 4-methyl-m-dioxane, MoO2(AcAc)2 has been found to be an overall superior catalyst to the others. Higher rate, yield, and comonomer incorporation have been obtained using MoO2(AcAc)2 as catalyst, although somewhat higher molecular weight copolymers have been obtained with
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140114
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  • 97
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    Poly(vinyl chloride-g-butyl rubber) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 153-157 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of poly(vinyl chloride-g-butyl rubber) and some of its physical properties are described. The key to the synthesis involves copolymerization initiation of an isobutylene-isoprene charge by a PVC/Et2AlCl initiator system with 1,2-dichloroethane as solvent. The graft is a thermoplastic; cast films are flexible and optically clear. Proof of grafting is the crosslinking with S2Cl2 of the pentane-extracted product in THF solution. Crosslinking the butyl rubber moiety in the graft reduces overall stress properties.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140115
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  • 98
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    PolyimidothioethersPaper presented in part at the 164th Meeting, American Chemical Society, New York, August 1972. (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 159-182 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The condensation of maleimide compounds with hydrogen sulfide and bisthiols was studied in several model systems. Bismaleimide compounds undergo rapid, exothermic polymerization with thiol-containing compounds in dipolar and basic solvents to give crosslinked polymidothioethers. Effective supression of the crosslinking reaction was achieved by carrying out the polymerization in the presence of a proton donor to inhibit anionic polymerization. A number of linear polyimidothioether homopolymers and copolymers were prepared and a study was made of their properties.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140116
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  • 99
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    Use of model compounds to determine equilibrium melting points of polymers (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2845-2852 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Evidence is given for the relationship \documentclass{article}\pagestyle{empty}\begin{document}$ T_m = T_m^ \circ \left[ {1 - 2RT_m \ln {{{\rm (}n)} \mathord{\left/ {\vphantom {{{\rm (}n)} n}} \right. \kern-\nulldelimiterspace} n}\Delta h} \right] $\end{document} describing the approximate dependence of the observed melting points Tm of oligomers on their degree of polymerization n, and its use in determining the equilibrium melting point T°m of the extended chain crystal and the heat of fusion Δh. Polyethylene and the n-alkanes, poly(ethylene oxide) and poly(methylene oxide), polyphenylene and other systems are considered.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170141201
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  • 100
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    Relaxation processes in mixtures of polymers with linear amides (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2867-2873 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Results of dynamic measurements of mixtures of polymer with linear low molecular amides are presented. New secondary relaxation processes that were revealed were elucidated by conformation motions of the amide group of low molecular compounds. The effect of water and similar substances on the character of low-temperature relaxation processes is also discussed.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170141203
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