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  • Physics  (1,072)
  • 2015-2019
  • 1980-1984  (1,072)
  • 1984  (555)
  • 1982  (517)
  • 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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    E-BOOK
  • 2
    Electronic Resource
    Electronic Resource
    Regular copolymers derived from bis(2-oxazolines). II.Part I, ref. 6. Synthesis of polyamides and polyamide-imides containing oxyethylene linkages (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 137-145 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New diamines containing amide and oxyethylene linkages were prepared by reduction of the corresponding dinitro compounds which were obtained by the reaction of p-nitrophenol with arylenebis(2-oxazolines) in dimethylformamide at 130°C. Moderate- to high-molecular-weight polyamides and polyamide-imides containing oxyethylene linkages were prepared by the polycondensation of the diamines with diacid chlorides and tetracarboxylic acid dianhydrides, respectively. The polyamides were soluble in dimethylacetamide containing 5% of lithium chloride and dichloroacetic acid, while the polyamide-imides dissolved only moderately in the latter solvent. Thermogravimetric analysis showed that thermo-oxidative decomposition started at 310-330°C and at around 325°C for the polyamides and polyamide-imides, respectively.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.170200115
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  • 3
    Electronic Resource
    Electronic Resource
    Some 1-substituted quaternary imidazolium compounds and related polymers: Qualitative and quantitative infrared analysis (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 783-793 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It was found that 1-substituted quaternary imidazolium compounds show some characteristic infrared (IR) activity. On quarternization of 1-substituted imidazoles strong absorption bands appeared at about 1150 and 1550 cm-1 in the IR spectra of these compounds. The band at 1150 cm-1 was assigned to the position 2 C-H bending mode and the 1550 cm-1 band was attributed to a ring vibration mode of the quaternary imidazolium compounds. The concentration of the quaternary imidazolium units in a polymer can be determined by measuring the intensity of the absorption bands at 1150 or 1550 cm-1 in relation to another suitable absorption band of the spectrum.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.170200316
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  • 4
    Electronic Resource
    Electronic Resource
    Polymerization of acrylamide initiated by the Ce4+/thiourea redox system (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 131-136 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of acrylamide (M) initiated by the Ce4+/thiourea (TU) redox system has been studied in an aqueous sulfuric acid medium at 35 ± 0.2°C under nitrogen atmosphere. The rate of polymerization is governed by the expression \documentclass{article}\pagestyle{empty}\begin{document}$$R_p = K_p [{\rm M}]^{1.20} [{\rm Ce}^{{\rm 4 +}}]^{0.5} [{\rm TU}]^{0.5}$$\end{document} The activation energy is 5.9 kcal deg-1 mol-1 in the investigated temperature range 30-50°C. The molecular weight is directly proportional to the concentration of monomer and inversely proportional to the catalyst concentration. With increasing concentration of DMF molecular weight decreases. The range of concentrations for which these observations hold at sulfuric acid concentration of 2.5 × 10-2 mol/L are [monomer] = 5.0 × 10-2-3.0 × 10-1, [catalyst] = (5.0-15.0) × 10-4, and [activator] = (1.0-6.0) × 10-3 mol/L.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.170200114
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  • 5
    Electronic Resource
    Electronic Resource
    Sulfonation and subsequent rections of ethylidene norbornane and dihydrodicyclopentadiene. The chemistry of some small molecule models for EPDM rubbers (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 875-896 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ionomers prepared by the sulfonation of EPDM rubbers have been the subject of considerable investigation with regard to their remarkable bulk and solution properties; however, relatively little is known about the chemistry of the sulfonation and the structure and subsequent reactions of the sulfonated intermediates. This article reports an effort to enlarge our understanding of sulfonate ionomers by examining the chemistry of small molecule analogs of the olefinic sites which are present in low concentrations in EPDMs. Ethylidene norbornane (ENBH) and dihydrodicyclopentadiene (DCPDH) were synthesized as models for EPDMs which use ethylidene norbornene and dicyclopentadiene as their respective termonomers. The sulfonated products from the two models were quite different, a sultone with a rearranged carbon skeleton being formed in the former case and a remarkable regiospecific sulfonic acid in the latter. Conditions necessary for hydrolysis and ammonolysis were established, the former proceeding essentially by a substitution mechanism, the latter via a retro-Wagner Meerwein elimination. Rate studies showed the importance of solvent effects in these sulfonation reactions which were attributed to a combination of site reactivity and acetylsulfate solubility. Mixed solvents were effective in improving reactivity while maintaining the solvency necessary for EPDM polymers. The results of this model study are being used as a guide in studies of EPDM polymers.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.170200323
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  • 6
    Electronic Resource
    Electronic Resource
    Radiation-induced graft copolymerization of mixtures of styrene and acrylamide onto cellulose acetate. I. Effect of solvents (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 939-950 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The grafting of styrene and acrylamide, from both their binary and unitary systems, on cellulose acetate film was studied by means of the cobalt-60 postirradiation grafting technique. The extent of grafting was found to be dependent on preirradiation dose, reaction time, and temperature, and the optimum conditions were evaluated. The effect of solvents, e.g., water, methanol, ethanol, isopropanol, and t-butanol were studied. The composition of the binary mixture as well as the nature of the alcohol used as the solvent were found to have a strong influence in modifying the course of grafting. Each component of the binary monomer mixture was found to sensitize the grafting of the other, when the former is present in relatively large concentration. The observed results are discussed in detail in terms of relative molecular reactivity and reactivity ratios.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.170200404
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  • 7
    Electronic Resource
    Electronic Resource
    Synthesis, polymerization, and copolymerization of lactam-substituted styrenes (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 987-995 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four new substituted styrene derivatives carrying lactam rings (2-pyrrolidone or 2-piperidone) in para position have been synthesized, namely 4-(2-oxo-3-methylene-pyrrolidinyl)styrene, 4-(2-oxo-3-methylene-piperidinyl)styrene, 4-(p-styryl)-2-pyrrolidone, and 4-(p-styryl)-2-piperidone. Their homopolymerization and copolymerization with styrene, methyl methacrylate, and acrylic acid have been considered. By ring opening of the side lactam groups, the homopolymers are transformed into the corresponding poly aminocarboxylic acids.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.170200408
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  • 8
    Electronic Resource
    Electronic Resource
    Rare-earth-metal-containing polymers. 5. Synthesis, characterization, and fluorescence properties of Eu3+-polymer complexes containing carboxylbenzoyl and carboxylnaphthoyl ligands (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1271-1278 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Partially 2-carboxylbenzoyl (1) and 3-carboxyl-2-naphthoyl (2) substituted polystyrene were prepared by the Friedel-Crafts reaction of polystyrene with corresponding dicarboxylic anhydrides. Europium (III) salts of (1) and (2) and the copolymer of 4-vinylbenzoyl 2′-carboxylbenzoate-di(2-benzoyl benzoate) and styrene (5) were prepared. Polymer (5) was prepared by the copolymerization of the Eu3+ salt of 4-vinylbenzoyl 2′-benzoate and 2-benzoylbenzoate (ratio 1:2) with styrene. The fluorescence emission intensity was measured on fine powder samples. The intensity of (5) increased linearly as the Eu content increased. However, for the 1 and 2 systems the intensity reached a maximum at a Eu content as small as 0.5 wt% and remained constant when further increases were made. This phenomenon was accounted for by steric hindrance and a decrease in the freedom of bond rotation, which prevent the formation of multiple coordination linkages between Eu3+ and the benzoate groups.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.170200510
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  • 9
    Electronic Resource
    Electronic Resource
    Diffusion-controlled vinyl polymerization. III. Free volume parameters and diffusion-controlled propagation (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1331-1344 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The values of the parameters that are necessary to compute the free volume changes accompanying polymerization were determined from viscosity data of concentrated polymer solutions. Relationships applicable above and below the glass transition temperature of the polymer were quantified. A general treatment of the variation of the propagation rate constant with free volume was postulated, based on the variation of the monomeric diffusivity with free volume. This, in turn, was related to the friction coefficient of a polymer chain segment, the values of which are readily available. A discussion of the reaction behavior in the last stage of polymerization and the occurrence of limiting conversion is also presented.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.170200515
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  • 10
    Electronic Resource
    Electronic Resource
    Amylose-polyester block copolymers (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 997-1009 
    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 amylose-polyester block copolymers is described. 2,3,6-Tri-0-allyl amylose was synthesized by amylose alkoxide and allyl bromide and hydrolyzed by hydronium ions to give an hydroxyl-terminated allyl amylose oligomer (HTAA). The allyl groups were isomerized with t-BuoK to yield the prop-1-enyl isomer (HTPA). The HTPA was capped with a diisocyanate. The HTPA prepolymer was reacted with hydroxy-terminated poly(ethylene-co-propylene adipate) and poly-(ethylene terephthalate) to form block terpolymers. Block terpolymer formation was demonstrated by intrinsic viscosity increases, gel permeation chromatographic results, and infrared (IR) and PMR spectroscopy. The products were depropenylated by HgCl2 to yield amylose block terpolymers. These polymers were readily degraded by α-amylase.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.170200409
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  • 11
    Electronic Resource
    Electronic Resource
    Complex formation between poly(ethylene oxide) and alkali picrates (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1389-1400 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction of poly(ethylene oxide) with alkali picrates in tetrahydrofuran and dioxane was studied by optical and NMR spectroscopy and conductance measurements. Evidence was found of the formation of two kinds of solvation complex, differing in the nature of the ion pairs involved. A strong anion effect on cation binding to the polyether was demonstrated.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.170200602
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  • 12
    Electronic Resource
    Electronic Resource
    Preparation and characteristics of photocross-linkable poly(vinyl alcohol) (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1419-1432 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of poly(vinyl alcohol) with styrylpyridinium and quinolinium salts which contain formyl group produced water-soluble photosensitive polymers. The sensitivity was high, although the content of the styryl groups was extraordinarily low. Spectroscopical studies revealed that the high sensitivity is due to the aggregation of photofunctional group in the polymer matrix which leads to cyclodimerization on exposure to ultraviolet (UV) light.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.170200605
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  • 13
    Electronic Resource
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    Functionalization of polystyrene. III. Synthesis of polymeric thiol reagents (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1469-1487 
    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 polymer-bound thiol reagents, supported on macroporous 4% divinylbenzene co-polymer (Amberlite XE-305), via three synthetic approaches is described: (i) Alkylation or acylation of XE-305 with 3-nitro-4-halogen-substituted benzyl chloride or benzoyl halide yielding 3-nitro-4-halobenzene-bound species, followed by substitution of the activated polymeric halogen atom with sulfur (see Scheme 1). (ii) Formation of a thiol ether by a direct substitution of an active polymeric halogen by reaction with benzylthiol, followed by chlorination, thiolation, and reduction (see Scheme 2). (iii) Attachment of a prepared tailor-made disulfide to aminomethyl function of a polymeric support, followed by reduction (see Scheme 3). The polymers were tested for their free-thiol content by 5, 5′-dithiobis(2-nitrobenzoic acid) (Ellman's reagent12) in DMF. Their thiolytic activity was investigated in the removal of 2-nitrophenylsulphenyl (Nps) group from Nps-protected amino acid (Scheme 4). Site-site interaction between the polymer-bound thiol with its activated halide precursor to yield polymeric sulfide during displacement reaction, and the interconversion of the polymeric thiols into polymeric disulfides at equilibrium or during reaction with Nps-amino acids, observed, and is attributed to the flexibility of the polymeric matrices.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.170200609
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  • 14
    Electronic Resource
    Electronic Resource
    Vinyl polymerization by lithium organocuprates (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1549-1557 
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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: Vinyl polymerizations initiated by lithium organocuprates under several conditions were investigated. It was observed that this catalyst was effective in the polymerization of specific monomers such as α,β-unsaturated nitrile and carbonyl analogues. The rate of polymerization was rapid but retarded by the addition of pyridine, nitrobenzene, or hydroquinone. Polymerization of methyl methacrylate (MMA) with lithium di-n-butylcuprate as initiator produces predominantly isotactic poly(methyl methacrylate) (PMMA) in toluene. The overall activation energy was estimated as 3.5 kcal/mol deg. Lithium di-n-butylcuprate exerts a higher stereoregulating effect on the addition of monomers than other organolithium initiators. It is proposed that polymerization proceeds via a coordinated anionic mechanism.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.170200615
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  • 15
    Electronic Resource
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    Piezoelectric polymer films. I. Synthesis and properties (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1587-1598 
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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 piezoelectrically active materials comprised of various co- and ter-polymers of tributyltin methacrylate (TBTM) and trimethyltin methacrylate (TMTM) are described. In this article films of the various polymer compositions were evaluated for tin content, glass transition temperature (Tg), and crystallinity or “ordering” of the amorphous phase. A brief theory of piezoelectricity in polymers will be given in Part II with a description of sample preparation, poling techniques, and the measurement system, as well as piezoelectric evaluation results.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.170200619
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  • 16
    Electronic Resource
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    Complexes of polyacids with poly(vinylbenzocrown ether)s and polyvinylbenzoglymes in water (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1629-1638 
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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: Insoluble complexes are formed in acidic aqueous media when poly(acrylic acid) (PAA) and poly-(vinylbenzo-18-crown-6) (P18C6) or polyvinylbenzoglymes are mixed. Complex formation results from hydrogen bonding between carboxyl groups and crown ether- or glyme-oxygen atoms as well as from hydrophobic interactions. The precipitation is pH dependent and was determined as a function of the ratio PAA to P18C6 or to polyglyme at different HCl concentrations in 10-4M solutions of polycrown or polyglyme. Precipitation is nearly quantitative in 0.01N HCl. The compositions of PAA/P18C6 precipitates were determined as a function of the initial PAA/P18C6 ratio in solution. The complexes with P18C6 can be solubilized in acidic media when crown-complexable cations (K+, Cs+, Ba2+) are added, but the charged P18C6 reprecipitates in basic solution as a polysalt complex with the PAA-polyanion. More stable PAA-P18C6 complexes in the form of fibers can be obtained by interfacial complex formation. Poly(methacrylic acid) is less effective as a complex former.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.170200623
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  • 17
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    Acrylonitrile-4-vinylpyridine copolymers effect of comonomer sequence distribution on properties (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1653-1667 
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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: Acrylonitrile-,4-vinylpyridine copolymers were prepared in chloroform solution at 60°C with AIBN as initiator. Copolymer compositions were determined from their 15.01-MHz 13C-NMR spectra. Reactivity ratios of rAN = 0.093 and r4VP = 0.32 were calculated by the Kelen and Tudos method. The run number, number-average sequence lengths, and monomer sequence distributions were also calculated. The Tg values of the copolymers, their dye uptake, and degree of alkaline hydrolysis were influenced by the overall copolymer composition but particularly by the monomer sequence distribution in the copolymers.
    Additional Material: 12 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.170200701
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  • 18
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    Effects of triphenylsulfonium hexafluorophosphate in the radiation-induced cationic polymerization of styrene (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1709-1716 
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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: Radiation-induced cationic polymerization of styrene was studied in methylene chloride in the presence of triphenylsulfonium hexafluorophosphate. Acceleration in polymerization and an increase in molecular weight at a low temperature (-78°C) were observed in the presence of triphenylsulfonium salt. A study of pulse radiolysis revealed that both effects are due mainly to PF-6, which forms ion pairs with the cationic species involved in the polymerization.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.170200705
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  • 19
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    Reaction rate of crosslinkings by using a metallated polymer. II. Intermolecular and intramolecular crosslinkings at the second state (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 2555-2564 
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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: Lithium-metallated styrene-p-benzylstyrene copolymer was reacted with the branched polymer with chlorine groups at the pendant chain ends (multifunctional branched polymer) in tetrahydrofuran (THF) at 25°C. The rate constant was estimated from the changes in the concentration of metallated polymer by using photometrical measurements. The various reaction conditions were chosen and it became clear that the rate constants of intermolecular (k20) and intramolecular (k3intra) crosslinkings were derived separately at the second stage. k20 showed a constant value in spite of the molecular weight of crosslinker chains and was about equal to the rate constant of the grafting. The rate of intramolecular crosslinking at the second stage increased with decreasing the molecular weight of pendant chains of multifunctional branched polymer.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.170200915
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  • 20
    Electronic Resource
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    Metal-acetylacetonate chelate crosslinked gels (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 2575-2602 
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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: Polymers containing pendant acetylacetonate (acac) groups suitable for crosslinking through metal complex formation are described. Diene-based copolymers, polystyrene, and polydimethylsiloxane, each containing a measurable number of acac groups distributed along the chains, were synthesized. The polymers were studied both for the amount of acac ligand and for their crosslinking reactions with selected transition metals by ultraviolet (UV) second-derivative spectroscopy. The UV analyses of the polymer systems were compared with their monomer analogs, and the results confirm that the crosslinking chelation reactions of polymer compounds are similar to those of model compounds. Homogeneous chelate crosslinking conditions were developed by using transition-metal salts such as Cu(laurate)2, Fe(laurate)3, and Cr(laurate)3 in solvents such as chloroform and benzene. Polymeric ligands containing 1-5% acac in solution at various concentrations were reacted to form both inter- and intramolecular crosslinkages. The kinetic stability of the chelate crosslinks has been studied by a unique ligand exchange-gel solubility relationship.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.170200917
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  • 21
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    Plasma polymerization of tetrafluoroethylene. IV. Comparison of ethylene and tetrafluoroethylene by measurement of electron temperature and density of positive ions (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1833-1846 
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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 double probe method was applied to plasma of tetrafluoroethylene (TFE) and ethylene and the electron temperature (Te) and density of positive ions (np) were measured at various discharge wattages. The probe current-probe voltage diagrams for TFE were different from those for ethylene. The shape of its diagram indicates that a considerable number of negative ions exist in TFE plasma. The levels of np for TFE were also nearly six times greater than those for ethylene at the same discharge current. The dependence of TFE polymer deposition and the chemical structure of the polymer, based on ESCA data on discharge current, was related to Te and np measured by the probe method. The values of Te and np may not be directly related to the polymer formation in a plasma; the method provides a direct measure of plasma energy density where plasma polymerization takes place, whereas it cannot be accurately estimated by the input energy of a discharge. It was found that plasma energy density based on (npTe) for TFE plasma and that for ethylene differ significantly at the same level of input parameter (W/FM), where W is the discharge wattage, F is the volume flow rate, and M is the molecular weight of the monomer.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.170200716
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  • 22
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    Alternating copolymerization of N-benzylidine aniline (NBA) with α-haloacrylic acids (XAA). IV. Synthesis, characterization, and kinetics (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1885-1897 
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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: This article describes a new, spontaneous, 1:1 alternating copolymerization between a Schiff base, N-benzylidine aniline (NBA), and α-haloacrylic acids (XAA) such as α-chloroacrylic acid (ClAA) and α-bromoacrylic acid (BrAA). The structure of the copolymers was identified by nuclear magnetic resonance (NMR) and infrared (IR) spectra. By using the isolation method we determined the order of each monomer. On the basis of kinetic studies, a mechanism that involves initiation, propagation, and termination by zwitterion is proposed. The effects of copolymerization under various conditions were studied and the intrinsic viscosity and number-average molecular weight were measured. The overall energy of activation, ERp, for the copolymerization was determined and thermal degradation studies were made.
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    URL: http://dx.doi.org/10.1002/pol.1982.170200720
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    Macromolecular N-nitroso-acylamines as photosensitizers for polyreactions. photochemical synthesis of block copolymers from polycondensates and olefinic monomersPart of a lecture presented at the GDCh Symposium on Photochemistry in Göttingen, Germany, 1979 (see ref. 1); fifth contribution on “N-nitroso-acylamines as initiators and photosensitizers for polyreactions” (see ref. 2).Dedicated to Professor Herman Mark on the occasion of his 85th birthday, but publication unfortunately had to be delayed. (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1935-1939 
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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: 1 Tab.
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    URL: http://dx.doi.org/10.1002/pol.1982.170200724
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    Syntheses of polyketones containing tricyclic fused rings and conversion to the polyamides in polyphosphoric acid (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1965-1970 
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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: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.170200731
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    Charge transfer interaction and electrical conductivity of poly(vinyl acetals) containing dispersed TCNQ radical anion salts (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 2765-2772 
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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: Charge transfer (CT) interaction is described in semiconducting dispersions of TCNQ complex salt \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm Et}_3 {\rm NH}^+ ({\rm TCNQ})_2^{\cdot^{\hskip-3.7pt\hbox{--}}}$\end{document} with and without added TCNQ°, in poly(vinyl acetal) matrices in which the electron-donor moiety is varied. The extent of CT interaction was determined in films and in solution (DMF, acetonitrile, or methylene chloride) through the absorbances at 398 nm (\documentclass{article}\pagestyle{empty}\begin{document}$ {\rm TCNQ}{\ }^{\cdot^{\hskip-3.7pt\hbox{--}}}$\end{document} and TCNQ°) and 857 nm \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm TCNQ}{\ }^{\cdot^{\hskip-3.7pt\hbox{--}}}$\end{document}. Resistivity of the conductive films was related to the stoichiometry of TCNQ species in the films and found to have a minimum at \documentclass{article}\pagestyle{empty}\begin{document}$[{\rm TCNQ}^\circ]/[{\rm TCNQ}{\ }^{\cdot^{\hskip-3.7pt\hbox{--}}}]\simeq 1$\end{document}. Lower resistivities were attained with films having a uniform, densely packed dispersion of microcrystallites which were obtained at a relatively slow solvent removal rate. With this particular complex salt, strong electron-donor polymers are found to be better matrices for semiconductivity.
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    Radical-initiated homo- and copolymerizations of methacryloyl fluoride (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 2829-2838 
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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 of methacryloyl fluoride (MAF) homopolymerization was investigated in methyl ethyl ketone (MEK) with azobis(isobutyronitrile) as initiator. The rate of polymerization (Rp) followed the expression Rp = k[AIBN]0.55[MAF]1.18. The overall activation energy was calculated as 74.4 kJ/mol. The relative reactivity ratios of MAF(M2) copolymerization with styrene (r1 = 0.083, r2 = 0.14), and methyl methacrylate (r1 = 0.48, r2 = 0.81) in methyl ethyl ketone were obtained. Application of the Q-e scheme (in styrene copolymerization) led to Q = 2.22 and e = 1.31. The glass transition temperature (Tg) of poly(MAF) was 90°C by thermomechanical analysis. Thermogravimetry of poly(MAF) showed a 10% weight loss of 228°C in air.
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    Free-radical synthesis of poly(urethane-g-N-vinyl pyrrolidone) (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 2879-2885 
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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: Relatively high-molecular-weight segmented polyurethanes based on methylene bis(4-phenyl-iso-cyanate), poly(propylene glycol), butane-1,4 diol, and cis-2-butene-1,4 diol have been synthesized and characterized. These unsaturated polyurethanes were successfully grafted using N-vinyl pyrrolidone as monomer and 2,2′-azobisisobutyronitrile as free-radical initiator. However, grafting experiments involving benzoyl peroxide as initiator were unsuccessful. The graft copolymers were isolated from the ungrafted polyurethane and poly(N-vinyl pyrrolidone) by selective solvent extraction. Elemental microanalysis, IR, NMR, thermogravimetric analysis, and equilibrium water sorption measurements were used to characterize the graft copolymers.
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    Effect of temperature conditions on the mechanism of formation, molecular structure, and properties of polyurethanes (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 2863-2878 
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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 formalized kinetic approach to the mechanism of urethane formation in the system of prepolymer with end NCO groups-1,4-butanediol together with the dispersion analysis of kinetic curves have helped to establish that, at moderate temperatures, the mechanism may be represented by a scheme comprising a noncatalytic stage of urethane formation and a catalytic one including the formation of a double complex of a catalyst with an isocyanate or a hydroxyl group. As the temperature rises the proportion of the noncatalytic stage decreases significantly, while a mechanism, including the formation of the triple complex isocyanate group-catalyst-hydroxyl, becomes the most probable. It has been shown that the formation of a triple complex at elevated temperatures is thermodynamically more advantageous than the formation of double complexes; hence these changes of mechanism with temperature. It has been found that the temperature conditions of polyurethane production greatly affect the degree of its branching. Two crosslinked polyurethanes were obtained, one under the temperature conditions providing for the minimum degree of branching, the other under isothermal conditions. It has been discovered that the degree of branching of a prepolymer may greatly affect the density of chemical and physical bonds and a range of physical and chemical properties of the polyurethane.
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    Kinetic models of homogeneous ionic polymerization (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 2915-2934 
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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: Based on modern concepts of ionic polymerization, a system of kinetic models which covers various initiation and propagation mechanisms, all based on a pseudo-steady-state assumption, is proposed. Special attention is given to the effect of solvent on the rate-controlling steps. Equations for reaction rate, degree of polymerization, and molecular weight distribution for 12 fundamental models are derived and fully discussed. The theory is also extended to more complicated systems such as the ion pair, free-ion system.
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    Noncyclic crown-type polyether polymers for transport of alkali cation and amino acid anion (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 2989-2993 
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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: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.170201023
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    Interaction of poly(vinyl acetate) radical with iron (III) complexes (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 3115-3120 
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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 vinyl acetate in N,N-dimethylformamide (DMF) at 60°C initiated by AIBN in the presence of [Fe(DMF)6](ClO4)3 and Fe(N3)3 had been studied. Fe(N3)3 was produced in situ by mixing solid sodium azide (NaN3) and hexakis(N,N-dimethylformamide) iron (III) perchlorate, [Fe(DMF)6](ClO4)3, in the ratio of 3:1. The velocity constant kx for the interaction of poly(vinyl acetate) radical with [Fe(DMF)6]3+ was found to be 1.44 × 103L mol-1 s-1 and that for the interaction of poly(vinyl acetate) radical with Fe(N3)3 to be 3.44 × 105 L mol-1 s-1 at 60°C.
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    Properties of low-molecular-weight polyethylene treated with gas plasma (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 3107-3114 
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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: Polyethylene films were evaporated in gas plasmas of Ar, N2, O2, and H2O. The deposits were analyzed by infrared (IR) spectroscopy to determine the concentration of characteristic functional groups. The deposit prepared in Ar-atmosphere had a rather high concentration of methyl group and many double bonds were produced in the film. The deposits prepared in Ar- and N2-plasmas produced similar spectra, which showed twice the concentration of methyl group than the deposit in Ar-atmosphere and also contained a few carbonyl and hydroxyl groups. The film treated in O2-plasma contained the largest amount of carbonyl group and the lowest number of double bonds among the plasma-treated deposits. Dielectric loss curves against temperature for the deposits treated in these plasmas showed a broad peak near 20°C. For O2-plasma-treated film the loss tangent curves showed a sharp maximum. The activation energy for the relaxation of Ar-, O2-, and H2O-plasma-treated films had the same value of 50.6 kcal/mol. The observed relaxation in the films prepared in gas plasmas was considered due to the β process and was attributed to the motion of oxidized branched polyethylene.
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    Ethynyl-terminated polysulfones: Synthesis and characterization (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 3131-3146 
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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: Hydroxy-terminated polysulfones (PSs) of number-average molecular weights from 3000 to 26,000 g/mol were converted to the corresponding 4-ethynylbenzoate-terminated PS through a three-step synthesis. The initial step involved the reaction of the hydroxy precursor with 4-bromobenzoyl chloride followed by displacement of the bromo group with trimethylsilylacetylene using a palladium catalyst. The trimethylsilyl group was subsequently cleaved with a weak base to afford the ethynylbenzoate-terminated PS. A more direct route to the ethynylbenzoate-terminated PS involved the reaction of the hydroxy-terminated PS with 4-ethynylbenzoyl chloride. The trimethylsilylethynyl and ethynyl groups undergo a thermally induced reaction to provide modified PS with better solvent resistance and higher apparent glass transition temperatures than an unmodified linear PS. The physical properties of the modified PS are compared with those of a linear PS.
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    URL: http://dx.doi.org/10.1002/pol.1982.170201109
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    Phase-transfer reactions catalyzed by phosphonium salts attached to polystyrene resins by spacer chains (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 3421-3429 
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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 of reaction of 1-halooctanes with aqueous sodium cyanide catalyzed by phosphonium salts attached to insoluble polystyrene resins by tetramethylene or heptamethylene spacers was studied as a function of catalyst particle size, degree of polymer crosslinking, percentage of ring substitution, and temperature. Rates of reaction of 1-bromooctane with 17-38% ring-substituted catalysts increased as spacer-chain length increased. Rates of reaction of 1-bromooctane decreased, whether the percentage of ring substitution increased or decreased from 17-19%. Rates of reaction of 1-chlorooctane increased with increasing spacer-chain length and decreasing percentage of ring substitution. Apparent activation energy for the reaction of 1-bromooctane with 9% ring-substituted, spacer-modified catalysts was 9-10 kcal/mol and 13 kcal/mol with 17-19% ring-substituted catalysts. The hydrophilicity of catalysts decreased with increasing spacer-chain length and decreasing percentage of ring substitution. The mechanisms of reaction were discussed in terms of intrinsic reactivity and intraparticle diffusion limitations on the reaction rates.
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    Poly(β-pinenes) carrying one, two, and three functional end groups. II. Syntheses and characterizationPart XX of New Telechelic Polymers and Sequential Copolymers by Polyfunctional Initiator-Transfer Agents (Inifers) (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 3229-3240 
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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: Conditions for the convenient synthesis of linear poly(β-pinenes) that carry one or two tert-chloro end groups (∼Clt) and three-arm star poly(β-pinenes) that carry three termini have been worked out. Specifically, the polymer with one ∼Clt end group was prepared by the H2O/BCl3 system, whereas those with two and three ∼Clt termini were prepared by the use of p-dicumyl chloride and sym-tricumyl chloride/BCl3 inifer combinations. The ∼Clt-terminated polymers were dehydro-chlorinated to yield the corresponding olefins. The molecular weights of the products were low enough to permit infrared (IR) and quantitative 1H-NMR investigations. Poly(β-pinene-b-tetrahydrofuran) diblock copolymers have been synthesized by inducing the polymerization of tetrahydrofuran (THF) by the Pβ—Clt/AgCF3SO3 initiating system.
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    Kinetics of isothermal degradation of poly vinyl bromide (PVBr). A typical case of “autocatalytic” thermal degradation (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 25-34 
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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 of thermal degradation of a sample of 46.0% isotactic polyvinyl bromide (PVBr) was studied in a static procedure. An integrated analytical method is presented for the estimation of rate constants. Reaction curves for the formation of hydrogen bromide (HBr) can be interpreted in terms of two concurrent first-order reactions; namely, with activation energies of 29.7 and 40.6 kcal/mol, respectively. The mathematical derivation does not involve an approximation; thus the accuracy of the procedure depends only on the experimentation. Good agreement between calculated and experimentally determined values of a series of characteristic kinetical parameters was obtained. The formation of HBr from PVBr was studied kinetically by a thermogravimetric programmed procedure at room temperature to 700°C. By this method it is possible to determine the activation energy of the stripping process of the main chain without knowing the form of the kinetic equation. The activation energy of 40.1 kcal/mol for the overall process was evaluated by the MacCallum and Tanner method. This dynamic heating developed two distinct temperature regions in which maximum rate loss occurred at characteristic temperatures. The first temperature region was associated with the quantitative evolution of 100% HBr molecules.
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    Polymerization photoinitiated by carbonyl compounds. IV. α-diketones and α-substituted alkanones (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 73-78 
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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 photoinitiation efficiency of the free-radical polymerization of methyl methacrylate and styrene by several carbonly compounds has been determined. The compounds considered were α-substituted ketones and α-dicarbonyl compounds. For the ketones, the initiation efficiency employing methyl methacrylate depends on the α substitution; the values obtained change from less than 10-3 (acetone) to 0.65 (3-hydroxy-3-methyl-2-butanone). All ketones are more efficient towards methyl methacrylate than styrene. This result can be explained in terms of triplet quenching by the last monomer. The results obtained employing α-dicarbonyl compounds do not conform to a simple pattern. In particular, benzil shows a considerably larger efficiency towards styrene than for methyl methacrylate. Since benzil is efficiently quenched by styrene, the initiation must involve the interaction of an excited benzil molecule and the monomer.
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    Reduction of electroactive polymers via polyelectron transfer processes at solid electrodes (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 109-118 
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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 reduction of an electroactive polymer at an electrode involves the transfer of a large number of electrons to a single molecule. A quantitative study of this process indicates whether the system behaves ideally. The electron transfer process in polyvinylbenzophenone and in polyvinylbenzophenone-co-styrene in N,N-dimethylformamide solution was investigated by voltammetry at a rotating disk electrode. It is concluded that benzophenone (BP) groups attached to the polymer backbone are noninteracting electroactive centers and that every BP group is reducible at the electrode. The relationship between limiting current and molecular weight was examined quantitatively for a series of polymers of low dispersity with molecular weights ranging up to 300,000, and with a controlled, varied content of electroactive groups. The diffusion coefficient was determined as a function of molecular weight from the electrochemical data, and was found to be in good agreement with the theoretical model based on transport properties. The dependence of the diffusion coefficient on concentration of polymer and on temperature were investigated and activation energies determined.
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    Photocrosslinking and photografting of vinyl polymers using poly(styrene-co-p-vinylbenzophenone-p′-tert-butyl perbenzoate) as a comonomer (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 147-157 
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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: Styrene has been copolymerized with low percentages of p-vinylbenzophenone-p′-tert-butyl perbenzoate (VBPE). The resulting copolymer has been used to make graft copolymer with methyl methacrylate using UV irradiation (366 nm). The grafting efficiency has been observed to increase with time of irradiation and percentage of VBPE in the copolymer. The copolymer has also been observed to crosslink efficiently with photochemical irradiation.
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    Comments on “(A) critical examination of the dissociation-association phenomena in the hexane solution of lithium polyisoprenyl” by M. SzwarcThe editors of the Journal of Polymer Science, Polymer Chemistry Edition, have made every effort to allow the dialog between Professors L. J. Fetters, M. Morton, and M. Szwarc to be as open and objective as possible. Competent and careful referees have made the task of judgment easier for the editors. Nevertheless, there are still major points of contention. Clearly, no resolution of certain conclusions seems possible. The editors of the Journal of Polymer Science, Polymer Chemistry Edition, believe that both parties have had an adequate opportunity to express their opinions. The editors have agreed that we will not publish any additional dialog on this problem. (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 199-204 
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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 note has appeared which seeks to question work from these laboratories (which appeared in 1964). The author of this recent paper attempts to demonstrate that the ΔH and ΔS values, based on our results, for the dissociation of the polyisoprenyllithium dimer “have no meaning.” This assessment ignores information in the literature. For similar reasons, other claims by the author of this recent paper are shown to be subject to scrutiny.
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    Polycondensation of diesters with hetero atom groups with hexamethylenediamine in the presence of polymer matrix (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 227-231 
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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 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.170200124
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    Aromatic polyamides. IV. Configurational analysis of poly(chloro-2,4-phenylene isophthalamide) by NMR (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 253-256 
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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: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.170200129
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    Phthalocyanine polymers. I. Poly[2,2′-(4,4′,4″-,4‴-metal phthalocyanino)-5,5′-bibenzimidazoles] as new high temperature resistant polymers (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 269-275 
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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 novel class of poly(metal phthalocyanino) benzimidazoles were prepared by the condensation reaction between metal (Cu, Co, and Zn), 4,4′,4″,4‴-tetracarboxyphthalocyanine, and 3,3′-diaminobenzidine. The reaction was investigated by melt and solution condensation methods. These polymers showed excellent thermal and thermooxidative stability and are noteworthy for their high char yield (86-90%) at 800°C in an anerobic atmosphere. Elemental analyses, spectra, and TGA studies were used to characterize these materials. Isothermal gravimetric analyses were carried out to determine their long-term thermal stability.
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    Preparation of phosphorus-containing polymers. XXVII. Polyester-imides that contain phenoxaphosphine rings (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 335-342 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New phenoxaphosphine-containing polyester-imides were prepared by the interfacial polycondensation of a dichloroformyl-phenoxaphosphine derivative containing a preformed imide ring with five bisphenols. The polymerizations, which were carried out in a chloroform-aqueous sodium hydroxide mixture, afforded polyester-imides with reduced viscosities of 0.60-1.55 dL/g in 61-95% yields. The preformed imide ring did not undergo hydrolysis under the polymerization conditions. Several of the polymers were soluble in chloroform and could be cast into flexible and transparent films. The phenoxaphosphine-containing polyester-imides have good thermal properties, exhibiting little decomposition below 400°C. They appear to be more thermally stable than phenoxaphosphine-containing polyesters, but are not as thermally stable as the corresponding polyimides and polyamide-imides. The order of thermal stability for phenoxaphosphine-containing polymers in air is polyimide ≳ polybenzoxazole 〉 polyamide-imide ≳ polybenzimidazole 〉 polyester-imide 〉 poly-1,3,4-oxadiazole ≳ polyamide 〉 polyester. The polyester-imides exhibited self-extinguishing behavior.
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    Quantitative NMR measurements in copolymers of vinylidene chloride and acrylonitrile: The effect of saturation and varying nuclear Overhauser enhancements (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 775-782 
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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: Spin-lattice relaxation times and nuclear Overhauser enhancements (NOE) for 13C nuclei in copolymers of acrylonitrile and vinylidene chloride were measured at 20.1 and 67.9 MHz. In the —CCl2— region of the spectrum T1 and NOE values of the various resonances are equal within experimental error and are invariant to changes in composition. The T1 and NOE values of the —CCl2— region, however, are not equal to those of the —CH— or —CN region. As a result compositions cannot be calculated by direct comparison of the areas in the —CCl2— region and either the —CH— or the —CN region. Discrepancies can be corrected for the —CH— resonances by multiplication of the area by an empirical constant. A similar constant for the —CN region is composition-dependent at 20.1 and 67.9 MHz. A chemical shift anisotropy mechanism is postulated as important for relaxation of the —CN resonances. The overall influence of variable T1 and NOE values on quantitative determination of polymer composition is considered.
    Additional Material: 3 Ill.
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    Polymerization of 3,3-bis(chloromethyl)oxacyclobutane catalyzed by MAl(C2H5)4 (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 897-899 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Tab.
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    Kinetics of simultaneous decrystallization and crystallization induced in high-modulus rayon by bromine water (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 929-938 
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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: Studies of the effect of aqueous Br2 solution on the fine structure of cellulose have shown that the accessibility of the cellulose is a complex function of the duration of treatment. Following immersion of rayon-cellulose in the Br2 solution, its accessibility is observed to increase until a peak is reached, after which the accessibility decreases with time. For higher temperatures and greater concentrations of Br2, a sharper peak and faster rates of increase and decrease of accessibility are obtained. In order to explain this behavior, a mathematical model of the kinetics is postulated involving two opposing first-order processes occurring simultaneously. One process describes the decrystallization of crystalline regions within the cellulose by opening intermediate linkages due to Van-der-Waals forces involved. The second process relates to the crystallization of the less-ordered regions. The rate constants for these processes are determined by fitting experimental curves to the postulated analytical expression with the aid of a digital computer program. Experiments carried out on high-modulus rayon showed that for this type of cellulose, the effect described above was very pronounced. From the calculated rate constants, the activation energies of the crystallization and decrystallization reactions were determined. The plots of the rate constants versus 1/T showed that a break occurs at 25°C, corresponding to a second-order transition point of cellulose. The energies of activation of the crystallization process are in the range of 7-9 and 10-13 kcal/mol in the temperature ranges 10-25 and 25-40°C, respectively. The activation energies of the decrystallization process are 13 and 18-24 kcal/mol in these temperature ranges.
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    Alternating copolymerization of α-methylstyrene and maleic anhydride (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 977-986 
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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: Alternating copolymers of α-methylstyrene (α-MeSt) and maleic anhydride (MAn) were prepared by free-radical-initiated polymerization in bulk, benzene, or butanone as solvents. By applying the generalized model described by Shirota and co-workers, the reactivity ratios k1c/k12 and k2c/k21 were calculated from the change of copolymerization rate with monomer feed at constant total monomer concentration. From the equation Rp = Rp(f) + Rp(CT) were calculated Rp(f) and Rp(CT), and it was found that in benzene the reaction proceeds predominantly by the addition of CT-complex monomers, while in butanone, cross propagation of free monomers predominates. Termination occurs predominantly by homotermination of α-MeSt macro free radicals, kt22, although the cross termination kt21 is also operative.
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    Polymerization of pyrrole by potassium persulfate (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1089-1095 
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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: Pyrrole reacted with potassium persulfate in aqueous media to form polymers or “pyrrole blacks.” The structure and molecular weight depend on the initial pyrrole/K2S2O8 ratio. An ESR line due to trapped electrons or free radical ions appeared at g = 2.0036 (width 3.6 G) in all products and its intensity decreased with an increase in initial concentration of potassium persulfate.
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    Grafting vinyl monomers onto nylon-6. VII. Graft copolymerization of methyl methacrylate onto nylon-6 fibers with acetylacetonate complex of vanadium ion (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1139-1141 
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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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    Studies on the kinetics of ceric-thiourea-initiated aqueous polymerization of methyl methacrylate. I. Mechanistic features in moderately acid solution (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1203-1211 
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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 of the aqueous polymerization of methyl methacrylate by a ceric-thiourea initiator system in moderately acid solution (pH 2.15) was studied. The rate of polymerization was proportional to 0.41 power of ceric concentration, 0.32 power of thiourea concentration, and 1.18 power of monomer concentration. The degree of polymerization was smaller than expected from the rate of polymerization. Initiation efficiency was less than one. There was no evidence of any ceric ion termination in the concentration range of 2.50 × 10-4-2.00 × 10-3M studied. The results are explained in terms of partial primary radical termination; the principal mode of termination, however, was bimolecular.
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    The role of chain transfer agents in the emulsion polymerization of styrene (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1261-1270 
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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 chain transfer agents on the nucleation and growth of polymer particles in the emulsion polymerization of styrene were examined extensively. The chain transfer agents used are carbon tetrachloride, carbon tetrabromide, and four primary mercaptans (C2, n-C4, n-C7, and n-C12). It is shown that with an increase in the amount of chain transfer agents charged the rate of polymerization per particle decreases progressively. The number of polymer particles formed, on the other hand, increases initially then decreases. These effects can be enhanced by using a chain transfer agent with higher values of chain transfer constant and solubility in water. It is also demonstrated that with increasing radical desorption from the particles, aided by chain transfer agents, the emulsifier dependence exponent for the number of polymer particles formed increases from 0.6 to 1.0 and the initiator dependence exponent decreases from 0.4 to 0. The effect of chain transfer agents on the nucleation and growth of polymer particles in the emulsion polymerization of styrene can be explained in terms of desorption of chain-transfered radicals from the polymer particles.
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    Copolymerization of β-pinene with styrene oxide and N-vinylpyrrolidone (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1279-1285 
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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 β-pinene with styrene oxide (SO) and β-pinene with N-vinylpyrrolidone (VP) was investigated by using SnCl4 in dichloromethane diluent at low temperature. Monomer reactivity ratios were evaluated for both copolymers at -80°C; these are r1(SO) = 2.979 and r2(β-pinene) = 0.002 and r1(VP) = 0.096 and r2(β-pinene) = 0.294.
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    Diffusion-controlled vinyl polymerization. II. Limitations on the gel effect (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1315-1329 
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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 is frequently observed that the gel effect in vinyl polymerizations decreases in intensity at about the 50-70% conversion level. This is apparent in both rate and molecular weight data. It is postulated that there should be a limitation on the decrease in the termination rate constant to explain this effect. As an extension of the general theory of chain length dependent termination behavior, a general treatment of the gel effect with a limiting value of the termination rate constant is presented. A specific model is proposed for this limited rate constant which is based on the simple consideration that as translational movement of macroradicals becomes increasingly difficult the contributions made by segmental motion derived solely from the propagation reaction will be the prevailing mechanism. The termination reaction changes from chain length dependent to chain length independent during this transition period.
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    Modification of the wettability of a poly(ethylene terephthalate) film treated by corona discharge in airManuscript complete November 1, 1981 (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1373-1387 
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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 wettability of poly(ethylene terephthalate) films is an important criterion for their industrial use. The attainment of that property is realized by treatment of the material under corona discharge. The purpose of this article is to describe the influence of the principal parameters of the discharge on the modification of the surface properties; the influence was measured by physicochemical methods (ESCA, contact angle). The results prove that the most important physical parameters of the discharge are the wire-cylinder distance, the current intensity, and the time of treatment. The analysis shows that the fixed species are oxygen and nitrogen in the form of carboxylic functions and amines or nitrogen oxides. In any case, the correlation between free surface energy and concentration of fixed chemical species shows that the surface properties depend on the chemical functions introduced into the material by the discharge.
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    Polymerization of cyclohexene oxide with aluminum complex-silanol catalyst. IV. Photopolymerization with Ph3SiCOPh-Al complex-alcohol catalyst system (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1433-1443 
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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 catalyst system (Ph3SiCOPh-aluminum complex-alcohol) was investigated for photopolymerization of cyclohexene oxide. Polymer conversion and molecular weight increased with polymerization time. When a Ph3SiCOPh-Al (n-Praa)3-alcohol catalyst system was used the catalyst activity decreased, depending on the alcohol: i-PrOH 〉 n-PrOH 〉 i-BuOH 〉 MeOH 〉 t-BuOH 〉 H2O. When the Ph3SiCOPh-Al complex-i-PrOH catalyst system was used the catalyst activity decreased, depending on the ligand of the Al complex: ß-ketoester 〉 orthocarbonyl phenol 〉 ß-diketone. Benzophenone derivatives were effective for catalyst activation as a photosensitizer.
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    Solvent effect on radical polymerization of butyl acrylate (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1489-1496 
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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 propagation and termination rate constants kp and kt for the radical polymerization of butyl acrylate initiated by biacetyl have been measured by using the rotating-sector method, in various solvents at 30°C. The value of kp and initiation rate Ri varied with solvents, while the value of kt did not change with solvents except for benzonitrile. The variation of kp with aromatic solvents has a trend against Hammett σp of the solvent substituents similar to that for methyl methacrylate or phenyl methacrylate except for the value in benzonitrile, when it is larger than the variation for methyl methacrylate or phenyl methacrylate. The larger variation of kp for butyl acrylate is compatible with the view that the origin of the solvent effect lies in complex formation between the propagating radical and aromatic solvent molecules. The exceptional decrease in kp and kt in benzonitrile is explained by a contraction of the poly(butyl acrylate) chain in the poor solvent.
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    Copolymerization of isobutene and α-methylstyrene as a function of reaction conditions (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1517-1532 
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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 influence of reaction conditions (solvent, Lewis acid, temperature) on the cationic copolymerization of isobutene and α-methylstyrene was investigated. The crude product consists of low molecular nonprecipitable oligomers, polyisobutene, and poly(isobutene-co-α-methylstyrene). The amount of poly(α-methylstyrene) formed under the reaction conditions used was negligible. The degree of charge separation in the propagating cationic intermediate determines the selectivity of the reaction; that is, incorporation of monomer units into the polymer, ratio of different product fractions, and microstructure. Molecular weight distribution, copolymerization parameters, and sequence-length distribution functions were determined. The softening range of the copolymers depended on their isobutene content but appeared to be constant up to 15% isobutene in copolymers. The degradation temperature of the copolymers was between 340 and 390°C.
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    Interaction of Tb(III) and hydrolyzed polyacrylamides in solution as a gel and in the solid state (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1569-1579 
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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: Formation of the HPAM-Tb3 complex in solution was observed in the intensification of Tb(III) fluorescence, viscosity, and light scattering. The interaction is dependent on the degree of hydrolysis of the copolymer and the pH of the solution. As the pH value increases, an intensification of the interaction and formation of a gel is observed. The latter was associated with the appearance of crosslinks in which terbium, or one of its hydrolysis products, works as a binding agent between chains. After drying, the characterization of the residues of the gels was effected by analytical determination (C, H, N, Cl, Tb), fluorescence, and infrared spectrophotometry. The analysis and fluorescence revealed the existence of particles of terbium hydroxide; the infrared spectrophotometry showed the binding of terbium (III) to carboxylate of the copolymer.
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    Template effects in chelating polymers (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1609-1622 
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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(4′-methyl-4-vinyl-2,2′-bipyridine) has been prepared as have various copolymers with divinylbenzene. When polymerization is carried out in the presence of metal ions (Ni2+, Co2+, Cu2+) a metal-containing copolymer is obtained which, when the metal ion is removed with acid, retains some memory of the original chelating metal.
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    Studies on stable free radicals. XIX. Copolymerization of N-oxyl biradical with α-chloro-p-xylyleneFor part XVIII see ref. 1. (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1639-1647 
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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: Copolymerization of N-oxyl biradical with α-chloro-p-xylylene was carried out by varying the feed ratio of α,α′-dichloro-p-xylene which was the precursor of α-chloro-p-xylylene. The structures of the obtained copolymers were determined spectroscopically. The results that the N-oxyl attacked the carbon-bearing chlorine atom of α-chloro-p-xylylene suggest a nucleophilic reactivity of N-oxyl radical. The copolymerization process was also discussed.
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    Solid-state polymerization of acrylamide and its derivatives complexed with some lewis acids. II. Radiation-induced in-source polymerizationAuthor corrected proofs received April 27, 1982 (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1775-1784 
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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: Radiation-induced solid-state polymerizations of complexes of N-tert-butylacrylamide, N-tert-amylacrylamide, and N-tert-hexylacrylamide with zinc chloride and zinc bromide have been studied. An accelerating effect of temperature and an inhibiting effect of oxygen on the polymerization process were observed. The activation energies have been established. The influence of monomer structure as well as the halide used on the polymerization rate have been discussed and some regularities have been pointed out. The polymers obtained show good solubilities in common solvents, which proves that they are not crosslinked.
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    Kinetics of polyesterification. II. Foreign acid-catalyzed dibasic acid and glycol systems (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1819-1831 
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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: Polyesterification of diacid and diol in the presence of the foreign acid p-toluene sulfonic acid as catalyst was carried out under constant reaction temperatures of 140-166°C (rather than at the usual constant oil-bath temperature) and at molar ratios r of diol to diacid of 1.2-3.5. The experimental data obtained do not fit conventional rate equations as they appear in the literature. On the basis of ion pair formation, consideration of proton transfer from acid to alcohol, variation in dielectric constant of the reaction mixture as conversion increases, and inclusion of reverse reaction due to presence of unremoved water, we proposed a reaction mechanism and rate equations. The rate equation fitted our experimental data quite well. In addition the self-catalysis (absence of foreign acid) also showed promise, as confirmed by the experimental data measured under constant reaction temperatures, which appear in Part I.
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    Laser-initiated polymerization of charge-transfer monomer systems (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1875-1884 
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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 laser-initiated polymerization of charge-transfer monomer complexes was investigated with a pulsed nitrogen laser and an argon laser. Several donor-acceptor monomer charge-transfer systems were screened for polymerization in different solvents. Polymerization by laser initiation was achieved in two of these systems; that is, 2-vinylnaphthalene/fumaronitrile and 9-vinylanthracene/fumaronitrile. The best polymer yields were obtained with the 2-vinylnaphthalene/fumaronitrile system in sulfolane solvent. The influences on the polymer yield and composition of solvents, varying focal path length, glass conditioning, initiation sources, environment, and monomer feed ratios were evaluated. Infrared (IR) spectral studies, gel permeation chromatography (GPC), and chemical analyses were performed to characterize the polymer products arising from the polymerization of 2-vinylnaphthalene/fumaronitrile in sulfolane. The polymer contained a high percentage of sulfolane (ca. 1/3 mol fraction), presumably arising from solvent transfer to the growing polymer chains during the propagation phase of the polymerization.
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    Grafting onto carbon black: Reaction of urethane prepolymer with carbon black surface (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1943-1946 
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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: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.170200726
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    Synthesis and characterization of certain polyhydrazides containing azo group in the main chain (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1959-1963 
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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: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.170200730
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    Emulsion copolymerization of styrene and methyl methacrylate (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1993-2006 
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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: Chain transfer constants to monomer have been measured by an emulsion copolymerization technique at 44°C. The monomer transfer constant (ratio of transfer to propagation rate constants) is 1.9 × 10-5 for styrene polymerization and 0.4 × 10-5 for the methyl methacrylate reaction. Cross-transfer reactions are important in this system; the sum of the cross-transfer constants is 5.8 × 10-5. Reactivity ratios measured in emulsion were r1 (styrene) = 0.44, r2 = 0.46. Those in bulk polymerizations were r1 = 0.45, r2 = 0.48. These sets of values are not significantly different. Monomer feed compcsition in the polymerizing particles is the same as in the monomer droplets in emulsion copolymerization, despite the higher water solubility of methyl methacrylate. The equilibrium monomer concentration in the particles in interval-2 emulsion polymerization was constant and independent of monomer feed composition for feeds containing 0.25-1.0 mole fraction styrene. Radical concentration is estimated to go through a minimum with increasing methyl methacrylate content in the feed. Rates of copolymerization can be calculated a priori when the concentrations of monomers in the polymer particles are known.
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    Synthesis and characterization of a new conjugated polymer: Polytrifluoromethylacetylene (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 2043-2051 
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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: Polytrifluoromethylacetylene (PTFMA) was synthesized from trifluoromethylacetylene (TFMA) using a PdCl2/DMF catalyst solution or the anionic initiator n-butyl lithium. Although PdCl2 proved to be an effective catalyst for the polymerization of TFMA, long reaction times and poor yields made characterization of the resultant polymer difficult. The use of n-butyl lithium, on the other hand, resulted in high yields of PTFMA in relatively short reaction times. The results of thermal analysis and the effects of n- and p-type doping on the electrical conductivity of the polymer are discussed.
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    URL: http://dx.doi.org/10.1002/pol.1982.170200807
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    Fire-resistant polyimides and copolyimides based on 1-[(dialkoxyphosphinyl)methyl]-2,4- and -2,6-diaminobenzenes (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1065-1076 
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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: Various phosphorus-containing polyimides were prepared by the reaction of 1-[(dialkoxyphosphinyl)methyl]-2,4- and -2,6-diaminobenzenes (1) with a tetracarboxylic dianhydride like pyromellitic dianhydride (PMDA) and benzophenone tetracarboxylic dianhydride (BTDA). In addition, copolyimides that contained approximately 3% phosphorus were prepared by the reaction of 1 and m-phenylenediamine (MPD) with the aforementioned tetracarboxylic dianhydrides. Elemental analysis, inherent viscosity, infrared (IR) spectroscopy, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) studies were performed to characterize the polymers. Their thermal properties were compared with those of the corresponding common polyimides. It was shown that the molecular weight and thermal stability of the polymers were reduced as the concentration of the phosphorus moieties increased. The fire-resistance of the copolyimides was evaluated by determining their limiting oxygen index (LOI) value. Copolyimides that contained about 3% phosphorus showed an LOI value approximately 30% higher, than the value of the corresponding common polyimides. In addition, a model diamic acid and diimide was synthesized by the reaction of 1-[di(2-chloroethoxyphosphinyl)methyl]-2,4- and - 2,6-diaminobenzene (DCEPD) with phthalic anhydride and characterized by elemental analysis, IR, proton nuclear magnetic (1H-NMR) spectroscopy, DSC, and TGA. The pyrolysis behavior of the model compounds was investigated by gas chromatography-mass spectrometry (GC-MS). A direct cleavage of the P—C bond and a possible rearrangement to diisocyanates occurred during their pyrolysis.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220507
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    Plasma polymerization of trifluoromethyl substituted aromatic compounds (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1123-1130 
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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: Thin film coatings were prepared by polymerizing trifluoromethyl-substituted aromatic compounds in a glow discharge with low power levels and medium pressures. Smooth, continuous films which are adherent and insoluble in conventional solvents were produced. A significant amount of the fluorine content from the monomer was retained in the polymer. The trifluoromethyl group was not removed by the plasma conditions and appeared in the film as trifluoromethyl and difluoromethylene groups. The films were slightly less wettable than those of the unfluorinated films.
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    Synthesis and conformation of asymmetric rigid polyamides (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1153-1177 
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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: Asymmetric polyamides from the reaction of either optically active trans-1,2-cyclopropanedicarboxylic acid (C3) or trans-1,2-cyclohexanedicarboxylic acid (C6) with 2,7-diazaspiro[4,4]nonane(DSN) were synthesized. The possible conformations of these polymers and their model compounds in 2,2,2-trifluoroethanol (TFE), water, methanesulfonic acid (MSA), and sulfuric acid were examined by circular dichroism (CD), NMR, viscosity, and dipole moment measurements. The racemic polyamides (±)C3·(±)DSN and (±)C6·(±)DSN exist in extended forms. No intrinsic viscosity changes were observed for these two polymers in TFE and MSA. Certain viscosity and spectral changes have been observed for the optically active polyamides, although no specific ordered conformations can be assigned. The optically active diacid units incorporated into the polymer give a conformation unique from the totally extended chain. CD studies seem to evidence some conformational differences among the polyamide derived from (+)C6 diacid and the optically active DSN. By changing the solvent from TFE to MSA a blue shift of the trough was observed for (+)C6·(±)DSN, a red shift for (+)C6·(-)DSN, and an inversion of the CD spectrum for (+)C6·(+)DSN polyamides. The results of the work with (+)C6·(-)DSN in dilute acid solution suggest that the rotation around the C-N bond is a relatively low-energy process. The spectral and intrinsic viscosity data are consistent with this suggestion. No drastic spectral changes have been observed for the C3·DSN polyamides by changing the solvent from TFE to MSA. The amide group in the C3·DSN polyamide and the corresponding model compound prefer a similar conformation with the carbonyl group bisecting the cyclopropane ring. The C3·DSN polyamide seems to exist in an extended form.
    Additional Material: 17 Ill.
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    Cationic grafting from carbon black. II. Polymerization of styrene initiated by CO+ClO-4 group on the surface of carbon black (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1515-1524 
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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 cationic grafting of polystyrene initiated by carbon black containing the CO+ClO-4 group was investigated. The introduction of CO+ClO-4 groups onto a carbon black surface was achieved by the reaction of AgClO4 with carbon black that contained a COCI group. The latter was introduced by the reaction of carboxyl groups with SOCl2. It was found that polystyrene chains could be grown from CO+ClO-4 groups on the surface of carbon black. Moreover, polystyrene was effectively grafted from carbon black: the grafting ratio at 20°C increased to 58% as conversion increased. Furthermore, the grafting ratio and molecular weight of ungrafted polystyrene decreased with an increase in polymerization temperature. These results were explained by the fact that the increasing temperature of the polymerization caused an increase in the rate of chain transfer reaction of the growing polymer chain to the monomer. The carbon black obtained from the reaction produced a stable colloidal dispersion in a good solvent for polystyrene.
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    Polymerization of alkyl allyl oxalates in the evolution of carbon dioxide at elevated temperatures (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1541-1550 
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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: Radical polymerization of several alkyl allyl oxalates, including methyl allyl oxalate (MAO), ethyl allyl oxalate, propyl allyl oxalate, butyl allyl oxalate, and octyl allyl oxalate, was conducted in the evolution of carbon dioxide at elevated temperatures, and was compared with the anomalous polymerization behavior of diallyl oxalate (DAO) discussed in our earlier articleA. Matsumoto, I. Tamura, M. Yamawaki, and M. Oiwa, J. Polym. Sci. Polym. Chem. Ed., 17, 1419 (1979).. The kinetic equations for the polymerization of alkyl allyl oxalate were derived following the kinetic treatment of the DAO polymerization by further consideration of the absence of cyclization of the growing polymer radical and the effective reinitiation by alkyl radical, and were then satisfactorily applied to the polymerization of MAO, as a representative alkyl allyl oxalate. The evolution of carbon dioxide in the polymerization of alkyl allyl oxalates was enhanced with the increase of bulkiness of the alkyl substituent, as a result of steric suppression of the propagation of the growing polymer radical.
    Additional Material: 9 Ill.
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    Plasma polymerization. XI. A comparison of the plasma polymerization of the isomeric perfluorinated diazines (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 17-28 
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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: Plasma polymers synthesized by inductively coupled RF techniques have been investigated as a function of operating parameters for the isomeric perfluorinated diazines (pyrazine, pyrimidine, and pyridazine). A combination of ESCA and microanalytical studies shows that plasma polymers are produced by rearrangement mechanisms: the C/F and C/N stoichiometric ratios are similar to those of the starting monomers over a range of operating parameters. A comparison of rates of formation of plasma polymer films reveals distinctive differences between the isomeric diazines that suggest that equilibration of valence isomers occurs on a substantially slower time scale than for isomeric fluorinated benzenes5-9 which, in general, polymerize at essentially the same rates. In contrast to the remarkably low critical surface tension of plasma polymers based on perfluorobenzenes (ca. 20 dynes cm-2), the plasma polymer films from the perfluorinated diazines which are initially hydrophobic become hydrophilic in contact with water droplets. This is attributed to the hydrolytic instability of films associated with the labilizing influence of nitrogen on nucleophilic displacement of fluoride which is a feature of the chemistry of monomers.
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    Water-soluble copolymers. VII. Cerium (IV) induced graft copolymerization of acrylamide and sodium-2-acrylamido-2-methylpropane sulfonate onto dextran (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 49-60 
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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: Studies were conducted on grafting of acrylamide (AM) and sodium-2-acrylamido-2-methylpropane sulfonate (NaAMPS) comonomers onto dextran utilizing Ce(IV) induced initiation. The effects of reaction temperature, the Ce(IV)/dextran ratio, and the AM/NaAMPS ratio on grafting yield were investigated. The graft copolymerization behavior can be explained by exchange of the AMPS anion with one of the ligands on the Ce(IV) initiator. Oxidative modification of the dextran substrate improved the yield of graft copolymer. The dextran-g-poly(acrylamido-co-sodium-2-acrylamido-2-methylpropane sulfonate) samples prepared by this method were characterized as to copolymer composition and molecular weight utilizing elemental analysis, dilute solution viscometry, and aqueous size exclusion chromatography. Relationships of molecular weight and charge density to kinematic viscosity and salt sensitivity are discussed.
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    Photoinitiation of cationic polymerization. III. Photosensitization of diphenyliodonium and triphenylsulfonium saltsFor Part II, see ref. 1. (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 77-84 
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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: Photoinitiated cationic polymerization by photosensitization of diphenyliodonium and triphenylsulfonium salts is shown to proceed by two distinct electron transfer process: (1) direct electron transfer from excited-state photosensitizers and (2) indirect electron transfer from photogenerated radicals. The efficiency of the former process is attributed to the instability of the reduction products (from diphenyliodonium and triphenylsulfonium salts), which dissociate in competition with undergoing energy-wastage reverse electron transfer. Amplification of photons in the production of protons (or other reactive cations) is postulated to account for the high quantum yields observed in the latter process. Potential advantages of utilizing the indirect redox process in the design of UV curable hybrid systems, which contain functionality for both radical and cationic polymerization, are noted. The results also provide evidence against the importance of triplet states of the onium salts in photoinitiator activity.
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    Attempted polymerization of substituted pipecolic acid NCA's: Dimerization and mechanism (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 107-120 
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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: Racemic and optically active N-carboxyanhydrides (NCA)s of 2-methyl- and cis-6-methylpipecolic acid, when subjected to polymerization conditions in solution or in bulk whether with “weak” or “strong” base initiators, resisted polymerization under all conditions tried. Instead, the NCA of 2-methylpipecolic acid gave the corresponding cyclic dipeptide and the NCA of cis-6-methylpipecolic acid formed the cyclic dipeptide derived from trans-6-methylpipecolic acid. The mechanism of dimerization of these NCA's was investigated. Evidence was provided for the proposed mechanism in which the active moiety is not a carbamate ion but an amino group. Methyl 2-methylpipecolate underwent an intermolecular SN2-type reaction upon heating, yielding equimolar quantities of methyl N-methyl-2-methylpipecolate and 2-methylpipecolic acid.
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    The effect of organic nitriles on the radiation induced polymerization of styrene (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 135-144 
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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 a range of 10 organic nitriles on the radiation-induced polymerization of styrene was studied. A dose rate of 4.4 rad s-1 was used. A rate of polymerization of styrene (1.744 mol L-1 of toluene solution) of 5.0 × 10-7 mol L-1 s-1 was found. With organic nitriles present (styrene:nitrile ratio of 1:0.28) the rate of polymerization increased. Rates in the range of 5.5 × 10-7 -5.2 × 10-6 mol L-1 s-1, depending on the nitrile present, were obtained. The polymers were partially characterized and evidence of involvement of each of the nitriles in the polymer chains was revealed. The increase in rate of polymerization has been attributed to the part played by nitrile radicals in the initiation of styrene polymerization. Radical yield values [as G(nitrile radical)] were derived from the relevant rate expressions. Values ranged from 2.7 to 49.5, depending on the particular nitrile. Corresponding values of G(nitrile radical) in the range of 5.1-129.4 were obtained by the manipulation of number-average molar mass data. Values of kpkt of approximately 2 × 10-5 L mol-1 s-1 were found. Trommsdorff types of effect are absent from these systems.
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    Radiolysis of resist polymers. IV. Poly(p-substituted-α-methylstyrene)s (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 213-223 
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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 parasubstituents on the radiation chemistry of poly(α-methylstyrene) (PMS) was compared for the fluoro (PFMS), chloro (PCMS), bromo (PBMS), isopropyl (PiPMS), and methoxy (PMeOM) derivatives. Radiolysis yields, ESR spectra, and GC—MS analysis of products were obtained. PMS and PFMS have similar low radiolysis yields, products, and product distributions. Only main-chain radicals which persist to 200° were observed. PCMS has increased values of Gs, Gx, and Gr. The product analysis results suggest that the presence of chlorine contributes to the primary process by dissociative electron capture and enhances the cleavage of α-methyl group. Irradiation of PBMS caused crosslinking and yielded few volatile products. PMeOMS and PiPMS gel readily by γ-irradiation and may be useful as negative radiation resists.
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    Organosilane polymers: Formable copolymers that contain methyl(β-phenethyl)silylene or cyclohexyl(methyl)silylene units (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 225-238 
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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 polysilane copolymers which contain the units in the title were prepared in high yield by sodium coupling the corresponding organodichlorosilanes in toluene. These copolymers are highly soluble in common solvents and can be drawn into fibers or formed into films by molding or casting. They are also photoactive.
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    The effect of N-substituents of hindered amine on photo-oxidation of polypropylene (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 277-281 
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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: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220126
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    A Mössbauer study of polymers prepared from polyvinylpyridine and ferric chloride or ferric nitrate (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 303-318 
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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: Iron-ion-containing polymers were prepared by reacting atactic polyvinylpyridine with ferric chloride or ferric nitrate in methanol solution. Molar ratios of Fe3+ to 4-vinylpyridine (Fe:PVP) were 1:2, 1:6, and 1:20. Three kinds of iron center were characterized from 57Fe Mössbauer spectra recorded over a temperature range of 4.2-290 K. Infrared (IR) spectra of the samples were measured also. All samples contained amorphous hydrated ferric-oxide particles that exhibited superparamagnetic behavior at low temperatures. The size of the clusters (102-103 iron atoms per particle) was estimated from the average blocking temperatures TBav, which is sensitive to the Fe:PVP ratio. For FeCl3:PVP preparations with Fe:PVP of 1:2, 1:6, and 1:20 TBav was 37, 10, and 〈4 K, respectively. A small proportion (〈10%) of high-spin ferrous iron centers was found in most samples. A third type of signal attributable to oxygen-bridged ferric dimers was found in FeCl3-PVP preparations with Fe:PVP of 1:2 or 1:6 but not in Fe(No3)3-PVP samples. This species is probably [Cl3Fe—O—FeCl3]2-. Interactions between the polymer and the various iron centers were weak.
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    Synthesis and characterization of poly(ethylene glycol) derivatives (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 341-352 
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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: Five general routes for the preparation of polyoxyethylene [generally referred to as poly(ethylene glycol) or PEG] derivatives are described. These routes are (1) nucleophilic displacements with the alkoxide of PEG, (2) nucleophilic displacement on PEG-tosylate, -mesylate, or -bromide, (3) reductive amination of PEG-aldehyde, (4) reductive amination of PEG-amine, and (5) nucleophilic displacements on the s-triazine derivatives prepared from s-triazine trichloride (cyanuric chloride) and PEG. Eighteen derivatives are prepared and potential applications to catalysis, cell purifications, and other areas are discussed briefly.
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    Solid-state polymerization of butadienes. Polymerization of salts of 6-amino-2,4-trans,trans-hexadienoic acid (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 391-406 
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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 6-amino-2,4-trans,trans-hexadienoic acid and various of its salts was studied in the solid state. Crystals of the hydrochloride and organic inorganic double halides with cadmium chloride, manganese (II) chloride, and iron(II) chloride were found to polymerize rapidly upon UV or γ irradiation. An erythro-diisotactic polymer is obtained in the form of extended chain crystals. The polymer behaves as an amphoteric polyelectrolyte. The kinetics and the mechanism of the polymerization as well as morphological changes during the solid state reaction are discussed.
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    ESCA and contact-angle studies of the surface modification of poly(ethylene terephthalate) film: Photooxidation and aging (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 419-428 
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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: ESCA and contact-angle (H2O and CH2I2) measurements are used to follow changes in the surface of poly(ethylene terephthalate) film photooxidized (254 nm radiation in O2) for varying times, followed by aging for as many as three weeks or washing with water. Photooxidation occurs uniformly throughout the outermost 50 Å of the film to give a surface stoichiometry that corresponds to C10O6.6. Oxidation produces mainly carboxyl (acid) and alcohol/phenol groups, carbonyls form after extensive treatment. Low molecular weight products formed by chain scission and oxidation are removed by washing and diffuse into the bulk when aged. Oxidized products in higher molecular weight chains are not removed by washing, but can diffuse into the polymer bulk or reorient because of their chain mobility; therefore they are directed toward the polymer bulk rather than the surface. Extended photooxidation produces a stable oxidized surface more resistant to aging changes. The results are compared with those obtained for poly(ethylene terephthalate) film oxidized in an electrical discharge.
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    Radical polymerization behavior of N,N-disubstituted acrylamide: Absolute rate constants for polymerization and copolymerization of N-acryloylpiperidine (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 463-473 
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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 absolute rate constants of propagation (kp) and of termination (kt) of N-acryloylpiperidine (NAPi) were determined by the rotating sector method in bulk; kp = 273 and kt = 1.79 × 107 L/mol s at 30°C. It was noted that kp for NAPi was 100 times smaller than that for N,N-dimethylacrylamide (DMAcAm). The absolute rate constants of cross-propagations for copolymerizations with common monomers were evaluated by combination of the kp value and the monomer reactivity ratios. Quantitative comparison of the rate constants with those of DMAcAm and poly(DMAcAm) radical shows that NAPi is as reactive as DMAcAm and the smaller kp value for NAPi is ascribable to much the lower reactivity of the poly(NAPi) radical. The large difference in reactivity of the polymer radicals is discussed in relation to the steric factor of the piperadino and the dimethylamino groups which seems to affect the capability of the carboxamide group to stabilize the polymer radical.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220217
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    Preirradiation grafting of N-vinyl-2-pyrrolidone onto poly(tetrafluoroethylene) and poly(tetrafluoroethylene-hexafluoropropylene) films (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 493-502 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Preirradiation grafting of N-vinylpyrrolidone (NVP) onto poly(tetrafluoroethylene) (PTFE) and poly(tetrafluoroethylene-hexafluoropropylene) (FEP) films was investigated. The influence of grafting parameters such as preirradiation dose, monomer concentration, and grafting temperature on the rate and grafting yield was studied. Different solvents were used for diluting the monomer and it was found that the aqueous monomer solution at a concentration of 80 wt% was suitable for this grafting system. However, the graft polymerization of NVP in benzene terminated within a short time without significant grafting yield. The dependence of the grafting rate on preirradiation dose and monomer concentration was 1.2 and 1.07 order, respectively, for grafting onto PTFE films and 1.1 and 1.2 order, respectively, for grafting onto FEP films. Arrhenius plots for grafting onto PTFE films showed a breaking point at ca. 35°C and the overall activation energies were calculated as 23.6 and 9.0 Kcal/mol below and above 35°C, respectively. For grafting onto FEP films, however, no break was observed in the Arrhenius plots; the overall activation energy was 11.9 Kcal/mol. The swelling behavior and electric resistance of the grafted materials were investigated.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220219
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    Linear polythioesters. VII.For VI of this series, see ref. 5. Products of interfacial polycondensation of 1,4-di(mercaptomethyl)-2,3,5,6-tetramethylbenzene with some aliphatic acid dichlorides (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1025-1033 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several polythioesters by interfacial polycondensation of 1,4-di(mercaptomethyl)-2,3,5,6-tetramethylbenzene with oxalyl, succinyl, adipoyl, suberoyl, and sebacoyl chlorides were obtained. To determine the optimal conditions for interfacial polycondensation, the influence of the following factors on yield and value of reduced viscosity were studied: type of organic phase, concentration of hydrogen chloride acceptor, the quantitative ratio of aqueous to organic phase, molar ratio of reagents; temperature of reaction, rate of acid chloride addition, and contribution of catalyst. Thorough studies were carried out only for polycondensation of the dithiol with adipoyl and sebacoyl chlorides. The structure of all polythioesters obtained under the model conditions was determined by elementary analysis and infrared spectra. Initial decomposition temperature, mass loss in percentage at the same temperature, maximum rate of decomposition, and mass loss percentage at 100-400°C were defined by thermogravimetric analyses. Chemical resistance of the polythioesters was determined by treatment with some organic solvents, mineral acids (concentrated and 10%), and sodium hydroxide (10 and 50%). Some mechanical and electrical properties of the polythioesters obtained from dithiol and adipoyl and sebacoyl chlorides were determined. The molecular weight was not measured because of the low solubility of the polythioesters.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220503
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    Anionic polymerization of norbornene trisulfide (exo-3,4,5-trithia-tricyclo[5.2.1.02.6]decane)Presented in part at the Fifth International Microsymposium, “Advances in Ionic Polymerization,” Prague, July 1982. (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1085-1095 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The anionic polymerization of norbornene trisulfide initiated with sodium thiophenoxide (sodium cation solvated with dibenzo-18-crown-6 ether) was studied. Polymers with high molecular weights were obtained (Mn up to 105, osmometrically). Molecular weights calculated for living polymerization conditions (i.e., one molecule of initiator yields one macromolecule) agree well with Mn measured by osmometry. 1H-NMR, 13C-{1H}-NMR, and Raman spectra of the polymer are given. Thermodynamics of polymerization in toluene solvent is described. Enthalpy ΔHss = -(1.39 ± 0.17) kcal mol-1 and entropy ΔSss = -(7.52 ± 0.55) cal mol-1 deg-1 coefficients of polymerization were evaluated from the temperature dependence of the equilibrium monomer concentration determined dilatometrically.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220509
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  • 90
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    Fire- and heat-resistant polymer based on maleimido-substituted 2,2-bis(anilino)-4,4,6,6-tetrakis-(4-aminophenoxy)-cyclotriphosphazene (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1141-1151 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A fire- and heat-resistant polymer was obtained by the thermal polymerization of bismaleimido-substituted 2,2-bis(anilino)-4,4,6,6-tetrakis-(4-Aminophenoxy)-cyclotriphosphazene. The thermal stabilities of the polymer were evaluated in nitrogen and in air by thermogravimetric analysis. This polymer was stable to 345°C and had char yields of 78% at 800°C in nitrogen and of 71% at 700°C in air. The structures of cyclotriphosphazene precursors and the polymer were characterized using Fourier-transform infrared and proton nuclear magnetic resonance spectroscopy.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220514
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  • 91
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    Photopolymerization of methyl methacrylate and styrene by a oxosulfonium ylide (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1187-1190 
    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.1984.170220517
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  • 92
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    Thermal transitions of poly(3,3-dimethylthietane) (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1197-1200 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220520
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  • 93
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    Phase-transfer reactions catalyzed by phosphonium salts bound to macroporous polystyrene supports (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1243-1250 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of reaction of alkyl halides with aqueous sodium acetate or cyanide catalyzed by phosphonium salts supported on insoluble polystyrene resins, and rates of ion-exchange of the chloride ion in the catalysts against the acetate ion, were studied as a function of catalyst particle size, the percentage of ring substitution, the morphology of polymer support, and distance between active site and polymer backbone. Rates of 1-bromooctane or benzyl chloride with macroporous, 7-25% ring-substituted catalysts increased with increasing ring substitution. Rates with macroporous catalysts increased as a heptamethylene spacer was introduced between the active site and the polymer backbone. Rates of ion-exchange with macroporous catalysts were facilitated with increasing ring substitution or by the introduction of the spacer chain. A relation between the catalytic activity of macroporous or microporous catalysts and ion-exchange rates under triphase conditions was discussed.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220604
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  • 94
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    Living reversible anonic polymerization of N,N-diethylamine-1,3,2-dioxaphosphorinan (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1251-1258 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization of the cyclic amide of PIII is described for the first time. The N,N-diethylamine-1,3,2-dioxaphosphorinan was shown to give living reversible polymerization with anionic initiators. Lithium and sodium derivatives were found to be inactive. 1H-, 13C-, and 31P-NMR indicated that the polymer strictly reflects the monomer structure and is formed without any isomerization, the polymer chain being $\rlap{--} ({\rm OP}\left( {{\rm NR}_{\rm 2} } \right){\rm O(CH}_{\rm 2} \rlap{--} )_3 )_n $. Initiation involves attack of the anion on the P atom. From the dependence of the equilibrium monomer concentration on temeprature ΔH1s = 1.5 ± 0.2 kcal·mol-1 and ΔS1s = 4.6 ± 0.6 cal·mol-1·°K-1.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220605
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    Interaction of α-poly-L-lysine and ε-poly-L-lysine with methyl orange and its homologs in aqueous solution: Results from dialysis and spectroscopic measurements (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1281-1289 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction of α-poly-L-lysine and ε-poly-L-lysine with methyl and ethyl orange was studied by equilibrium dialysis and spectroscopic methods. The results of the dialysis measurements indicated that the extent of binding by ε-polypeptide is substantially higher than that by α-polypeptide, despite the much greater molecular weight of the latter. This difference in binding affinity was interpreted in terms of the increased conformational adaptability of ε-polypeptide because of its highly flexible structure. Furthermore, ε-polypeptide exhibited strong cooperative binding. In addition, the effect of the successive addition of α- and ε-polypeptides on the absorption spectra of methyl and ethyl orange was investigated. The addition of α-polypeptide with a molecular weight of 400,000 produced a new absorption peak at a shorter wavelength, due to the stacked dye molecules on the polypeptide chain, whereas that of ε-polypeptide did not. From the results of spectroscopic measurements a possible mode of interaction between these two polypeptides and the small molecule is discussed.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220608
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    Graft polymerization of acrylic monomers onto starch fractions. III. Effect of carbohydrate structurePresented in part at the Macro '83, 29 Symposium of IUPAC. (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1327-1333 
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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: Grafted PMMA was isolated by the acid hydrolysis method. Weight-average and number-average molecular weights were determined by gel permeation chromatography. The number-average molecular weight of the grafted chains was about 475,000 for amylopectin and 403,000 for amylose. The number of grafted chains (mmol) ranged from 2.4 × 10-3 to 4.6 × 10-3 for amylopectin graft copolymers and from 2.9 × 10-3 to 6.8 × 10-3 for those of amylose. These results were related to others obtained from ceric ion consumption studies. The values suggest that amylopectin, because of its complex structure, favors a higher consumption of ceric ion in homopolymerization reactions and inhibits the initiation reactions of the copolymerization.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220613
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    Morphology of core-shell latex particles (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1365-1372 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The progressive dissolution of carboxylated latex particles with increasing pH was utilized to investigate the internal structure of core-shell latex particles, in comparison with that of copolymeric latex particles formed from the same monomers. The results indicated that in those latex particles which are formed when ethyl acrylate (EA) -methacrylic acid (MAA) or methyl acrylate (MA) -MAA mixture is polymerized in the presence of poly(MA-MAA) or poly(EA-MAA) seeds the shell is composed of the more hydrophilic poly(MA-MAA) molecules relatively high in MAA content and the core is composed of both poly(MA-MAA) and poly(EA-MAA) molecules, regardless of the order of the stage feed, while the copolymeric latex particles are relatively uniform from surface to center in distribution of all components except MAA. Examination of the distribution of the carboxylic groups in all of the latex particles showed their concentration to be highest at the surface and to decrease with proximity to the center in accordance with other findings reported in the literature.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220617
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    Emulsion polymerization of styrene. III. Effect of Ti(III) and Cl(1) on the polymerization of styrene initiated by potassium persulfate (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1409-1417 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The emulsion polymerization of styrene initiated by potassium persulfate catalyzed by Ti+3 ions was studied. Two sources of Ti+3 ions were used: the titanium trichloride and titanium sulfate. It was found that the titanium ions used in conjunction with potassium persulfate decrease both the reaction rate and the average molecular weight. An even greater drop of reaction rate was noted when chlorine anions (TiCl3) were present. The presence of these ions had a stabilizing effect on the polydispersity.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220621
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  • 99
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    Mass spectroscopy of epoxylated novolac resin cured with phthalocyanine tetraamines (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1471-1479 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mass spectroscopy was done at different temperatures on epoxylated novolac resin DEN 438 (Dow Chemical Co.) alone, and after curing with various metal(II) phthalocyanine tetraamines (MPTA). Possible modes of fragmentation are given to explain the experimental results. Gas-chromatographic/mass-spectroscopic (GC-MS) analyses of MPTA derivatives indicated the presence of only trace quantities of benzene, aniline, cyanobenzene, and orthodicyanobenzene. The GC-MS studies of the cured DEN 438 epoxy resins indicated that the mechanisms of thermal degradation are qualitatively similar, and some common features were observed in their fragmentation in an electron beam and by thermal degradation. This study is a further assessment of the utility of these phthalocyanine derivatives for curing epoxy resins to produce heat-resistant polymer systems.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220625
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    Vinyl polymerization. 422. Initiation mechanism of uncatalyzed polymerization by polyethyleneglycol (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1507-1514 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The initiation mechanism on the radical polymerization of vinyl monomers by polyethyleneglycol (PEG-300) in aqueous solution was studied. The initiating radical species were determined by means of the spin trapping technique. They were concluded to be generated by the hydrogen atom transfer from the monomer adsorbed at the ether group of PEG-300 to the free monomer.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220629
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