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  • 101
    Electronic Resource
    Electronic Resource
    Synthesis and characterization of some new polyimides (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2105-2109 
    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.1981.170190822
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  • 102
    Electronic Resource
    Electronic Resource
    Polymerization of acrylonitrile initiated by K2S2O8-Fe(II) redox system (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2115-2118 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1981.170190824
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  • 103
    Electronic Resource
    Electronic Resource
    Kinetic relationships and mechanism of ozone reaction with polystyrene in CCl4 solution (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2175-2184 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this work a study is made of the degradation on ozonation of unfractionated polystyrene (PS) in CCl4 solution. It was found that the ozone attack of PS molecules is accompanied by hydrogen abstraction from tertiary CH bonds and by the formation of ozonides due to the reaction of ozone with the aromatic rings. A scheme of PS degradation in solution is suggested; several kinetic parameters are evaluated.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1981.170190905
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  • 104
    Electronic Resource
    Electronic Resource
    Water-soluble copolymers. III. Dextran-g-poly(acrylamides) control of grafting sites and molecular weight by Ce(IV)-induced initiation in homogeneous solutions (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2229-2241 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Model graft copolymers were synthesized by grafting acrylamide onto dextran (Mw = 500,000) utilizing an initiation method in which a Ce(IV)/HNO3 solution was added to the dextran solution in order to allow coplexation prior to monomer addition. Three synthetic reaction parameters were optimized on the basis of conversion and solution viscosity: monomer concentration, dextran concentration, and nitric acid concentration. Molar ratios of [Ce(IV)]/[dextran] were changed systematically to affect the number and length of the acrylamide grafts. The number of grafting sites and graft chain lengths, determined by selective hydrolysis of the carbohydrate backbone, were in good agreement with those theortically predicted from knowledge of initiation efficiency and monomer conversion. Rheological studies of the model graft copolymers were conducted in aqueous solutions as a function of temperature, added salt, and copolymer concentration.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1981.170190909
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  • 105
    Electronic Resource
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    Preparation and properties of some cardopolyamides (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2275-2285 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several polyamides that contained cardo units were prepared. Thus 9,9-bis(4-aminophenyl)fluorene and 9,9-bis(4-aminophenyl)anthrone were condensed with 2,5-dimethyl-1,4-benzenediacetyl chloride, 2,4-dimethyl-1,4-benzendiacetyl chloride, and 2,5-dimethoxy-1,4-benzediacetyl chloride. Lowtemperature solution polycondensation in dimethyl acetamide (DMAc) was used throughout. The polymers were obtained in 80-90% yield and possessed intrinisic viscosities in the range of 0.6-1.2. The polymers were characterized by infrared (IR) spectra and elemental analysis. The solubility, crystallinity, and thermal stability of the polyamides were also determined.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1981.170190913
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  • 106
    Electronic Resource
    Electronic Resource
    Graft copolymerization of anhydro sugar derivatives from macromolecular halides (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2313-2329 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cationic graft copolymerizations of bicyclic acetals, 1,6-anhydro-2,3,4-tri-O-benzyl-β-D-glucopyranose (LGTBE) and 1,6-anhydro-2,3,4-tri-O-methyl-β-D-glucopyranose (LGTME), were investigated with macromolecular carbenium ions formed from polymers that contain reactive halogens. Macromolecular complex catalysts formed from chlorosulfonated polyethylene or poly(isoprene-co-chloromethylstyrene) by the action of phosphorus pentafluoride yielded graft copolymers with low proportions (0.6-16%) of poly(LGTBE) or poly(LGTBE-co-epichlorohydrin) branchings. It was found that macromolecular complex catalysts formed from poly(styrene-co-fluoromethylstyrene) or poly(methyl methacrylate-co-fluoromethylstyrene) by the action of boron trifluoride etherate give graft copolymers with high proportions (up to 80%) of poly(LGTBE) or poly(LGTME) branchings. In addition, the model reactions for the graft copolymerization of LGTBE were examined with organic halide-PF5, organic halide-AgPF6, and organic fluoride-BF3·OEt2 catalytic systems, of which the last two indicate that the polymerization is effected by a carbenium ion mechanism.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1981.170190917
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  • 107
    Electronic Resource
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    Preparation of hexanoyl, decanoyl, and dodecanoylchitin (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2361-2363 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1981.170190921
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  • 108
    Electronic Resource
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    Head-to-head vinyl polymers. IV. Preparation and characterization of equimolar head-to-head copolymers of acrylic acid and its esters (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2391-2403 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The alternating copolymer of ethylene with maleic anhydride was esterified with a number of aliphatic alcohols to yield its monoesters, which correspond structurally to equimolar (1:1) head-to-head (h-h) copolymers of acrylic acid with alkyl acrylates. In addition, they were methylated with diazomethane to 1:1 h-h copolymers of methyl acrylate with alkyl acrylates. For comparison the 1:1 head-to-tail (h-t) copolymers of methyl acrylate with alkyl acrylates were prepared by radical copolymerizations. Some chemical, physical, and thermal properties of these 1:1 h-h and h-t copolymers were evaluated and compared. The softening and glass transition temperatures of the 1:1 h-h copolymers were somewhat higher than those of the corresponding 1:1 h-t copolymers, which indicated that the h-h replacements made the polymer chain stiffer and less flexible. The 1:1 h-h copolymers were also observed to degrade thermally at somewhat higher temperatures and with higher rates than the 1:1 h-t copolymers. The ratio of alcohol to monomer found in the pyrolysis products was higher for the 1:1 h-h than for its respective 1:1 h-t copolymer.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1981.170191003
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  • 109
    Electronic Resource
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    Spectral and thermodynamic studies of the interaction of binding site probes with poly(vinylpyrrolidone) (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2427-2441 
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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 binding of two ionic azo dyes (4-phenylazo-1-naphthol mono-and disulfonate) and a fluorescent probe (2-p-toluidinonaphthalene-6-sulfonic acid, TNS) to poly(vinylpyrrolidone) (PVP) was studied to obtain information on the nature of the interaction, binding isotherm, and binding site. Sorption of the dyes followed a Langmuir isotherm only at low polymer saturation. Apparent cooperativity in binding was seen at higher saturation. The polymer had a higher intrinsic binding constant but lower binding capacity for the doubly charged dye than for the structurally similar singly charged dye. Both dyes consisted of tautomeric mixtures of hydrazone and azonaphthol forms in equilibrium in the bound and unbound state. The preferential binding of the azonaphthol tautomer of the disulfonate was highly exothermic and accompanied by an entropy decrease. The binding of the hydrazone form was less favored by 1.8 kcal/mol, was weakly exothermic, and accompained by an entropy increase. Increased preference for the azonaphthol tautomer accompanied chain extension from charging the polymer. Chain extension had no effect on the emission frequency of bound TNS. Large differences in binding capacities for similarly charged dyes indicated the existence of specific dye-site interactions. Arguments are presented against nonspecific hydrophobic interactions as predominant forces responsible for binding.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1981.170191006
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  • 110
    Electronic Resource
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    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 
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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: 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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  • 111
    Electronic Resource
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    Vinyl polymerization. 403. Polymerization of vinyl monomer initiated with sodium poly-p-vinylphenolate (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2561-2569 
    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 vinyl monomer initiated by poly-p-vinylphenol (PVPh) in NaOH aqueous solution was carried out at 85°C with shaking. Methyl methacrylate (MMA) was polymerized, whereas styrene and acrylonitrile were not. PVPh, which is dissociated into phenolate form (PVPh-Na+) in NaOH aqueous solution, was effective for the polymerization. The effects of the amounts of MMA, PVPh, NaOH, and H2O on the conversion of MMA were studied. The rate of polymerization of MMA increased with an increase in the molecular weight of PVPh-Na. The overall activation energy was estimated as 54 kJ mol-1. The polymerization proceeded through a radical mechanism. The addition of tetra-n-butylammonium bromide increased the rate of polymerization.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1981.170191016
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  • 112
    Electronic Resource
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    Microstructure of vinyl acetate-butyl acrylate copolymers studied by 13C-NMR spectroscopy: Influence of emulsion polymerization process (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2619-2633 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The compositions and sequence distributions of vinyl acetate-butyl acrylate copolymers obtained with batch and semicontinuous emulsion polymerizations have been studied by 1H and 13C NMR. The batch process gives heterogeneous copolymers while with the semicontinuous one the sequence distribution is statistical. These differences in sequence distributions have been related to the physical properties of the copolymers.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1981.170191021
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  • 113
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    Synthesis and characterization of new poly(ether urethanes) (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2651-2654 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1981.170191024
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  • 114
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    Aromatic polyesters obtained directly from hydroxybenzoic acids by hexachlorocyclotriphosphatriazene (PNC) in pyridine (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2681-2687 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyaryl esters of moderate molecular weights were prepared by the direct polycondensation reaction of hydroxybenzoic acids and its derivatives with hexachlorocyclotriphosphatriazene (also known as phosphonitrilic chloride trimer, PNC) as a condensing agent in pyridine. Copolymerization of p-hydroxybenzoic acid with several hydroxybenzic acid derivatives was carried out to improve the processability of the polymer of p-hydroxybenzoic acid, which yields fusible and soluble copolymers of high inherent viscosities. Polymer solubility and thermal behavior were examined.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1981.170191103
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  • 115
    Electronic Resource
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    Cationic polymerization by aromatic initiating systems. IV. Synthesis and characterization of α-ω-diphenylpolyisobutyleneA preliminary report concerning this research has appeared: J. P. Kennedy and D. Y. L. Chung, Polym. Prepr. Am. Chem. Soc. Div. Polym. Chem., 21, 150 (1980). (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2729-2735 
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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 isobutylene using ø3Al coinitiator and the tertiary chlorides tert.-butyl chloride (t-BuCl) and 2,6-dichloro-2,6-dimethylheptane (Clt-R-Clt) initiators has been studied. Polymerization rates with the t-BuCl/ø3Al and Clt-R-Clt/ø3Al initiating systems were high in the -20 to -70°C range. Yields and molecular weights increased with decreasing temperature. As predicted by model experiments the extent of phenylation increases with decreasing temperatures. According to spectroscopic evidence the polyisobutylenes carry phenyl end groups.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1981.170191107
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  • 116
    Electronic Resource
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    Kinetics of polymerization of acrylonitrile initiated by acidic permanganate/thioacetamide redox system (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2759-2764 
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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 vinyl polymerization of acrylonitrile (AN) initiated by an acidic permanganate/thioacetamide (TAm) redox system have been investigated in aqueous media at 30 ± 0.2°C in nitrogen, and the rate of polymerization measured. The effect of additives like organic solvents, neutral electrolytes, and complexing agents on the rate have been assessed. Based on the experimental results, a suitable reaction scheme involving initiation by organic free radicals generated by the interaction of Mn(IV) with protonated thioacetamide and termination by Mn(III) has been suggested. Various rate and energy parameters have been evaluated.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1981.170191111
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  • 117
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    Aromatic polyamides. II. Thermal degradation of some aromatic polyamides and their model diamides (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2817-2834 
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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: Thermal degradation behavior of poly(1,3-phenylene isophthalamide) and poly(chloro-2,4-phenylene isophthalamide) was investigated with the aid of some appropriate model compounds. The pyrolysis products of these materials were identified by gas chromatography (GC), gas chromatography/Fourier transform infrared spectroscopy (GC/FT-IR), and gas chromatography/mass spectrometry (GC/MS). The residual chars were characterized by IR spectroscopy. Thermogravimetric analysis (TGA) was applied to study the effect of end-group concentration on the degradation characteristics of the two polyamides. Kinetic parameters that describe the thermal degradation of the polyamides were also evaluated by TGA. The results of this investigation suggest that the thermal decomposition of these aromatic polyamides involves homolytic as well as hydrolytic cleavages of the amide units.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1981.170191115
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  • 118
    Electronic Resource
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    Poly[trans-1-(3-vinyl-9-carbazolyl)-2-(9-carbazolyl)cyclobutane]. Synthesis and comparison with poly(9-ethyl-3-vinylcarbazole) (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2861-2868 
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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: Trans-1-(3-vinyl-9-carbazolyl)-2-(9-carbazolyl)cyclobutane(I) was synthesized. Homopolymerization of I and copolymerization with 9-ethyl-3-vinylcarbazole(II) were conducted cationically. It was found that I polymerized to high molecular weight polymers (〈 105) with good yields, although its polymerizability was lower than that of II. Copolymer composition was determined by gel permeation chromatology (GPC) analysis, based on the remaining monomer ratio. Fluorescence spectroscopy indicated that poly(I) did not form excimer. Excimer emission gradually appeared with increasing II content in poly(I-co-II) to the homopolymer of II. This difference between poly(I) and poly(II) was attributed to the crowded and sterically distorted chromophore assemblies in poly(I). 1H- and 13C-NMR spectroscopy of cyclobutane groups in poly(I) compared with that in the monomer model compound supported the conclusion derived from fluorescence study.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1981.170191119
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  • 119
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    Models for polyesterification kinetics. I. Esterfication kinetics in polar medium (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2905-2918 
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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 reaction of 1-octadecanol with octadecanoic acid and w-carboxy polyxyethylene with w-hydroxy polyoxyethylene in the absence of a cataylst were studied as models of polyesterification. Both rreactions are third order. Order two in acid and one in alcohol have been experimentally established by studies of nonstoichiometric systems. These results are not in agreement with recent work related to polyesterification kinetics. The mechanism involves autocatalysis by the acid and the presence of nondissociated ion pairs. Activation enthalpies and entropies are given.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1981.170191123
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  • 120
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    Plasma polymerization of tetrafluoroethylene. III. Reproducibility and effects of substrate and reactor materials (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2937-2946 
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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 polylmerization occurs in plasmas surrounded by surfaces and polymer formation is one of the complicated interactions that take place between active species and molecules which constitute surfaces and gas phases. Effects of reactor wall, substrate materials, flow rate, and discharge power on polymer formation, and properties of polymer deposits were investigated by ESCA, IR (infrared) spectroscopy, and the measurement of system pressure. The effect of surface is important at the initial stage of plasma polymerization which can be easily detected by the system pressure change; however, integrated properties such as IR spectroscopy and the deposition rate show the effect in a less pronounced manner. ESCA, which reflects the properties of surface (approximately 20 A˚ in depth), showed the effect of surface in an even less sensitive manner. The amount and properties (including the effects of surfaces) are dependent on plasma polymerization parameter W/FM(W, wattage; F, volume flow rate; and M, molecualar weight of monomer) and the location of deposition within a reactor. IR and ESCA data clearly showed the dependence of polymer properties on W/FM; i.e., increase of W and decrease of M to be equivalent. When all these factors were kept under control, the reproducibility of plasma polymerization was found to be excellent.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1981.170191126
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  • 121
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    Synthesis of carbon-carbon chain polymers by phase-transfer-catalyzed polycondensation of phenylacetonitrile with activated dichlorides (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2997-3003 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two-phase polycondensation of phenylacetonitrile with α,α′-dichloro-p-xylene and other activated dichlorides in an aromatic solvent-aqueous sodium hydroxide system with various phase-transfer catalysts produced carbon-carbon chain polymers with inherent viscosities up to 0.6 dL/g. Reaction variables of the polycondensation are discussed in some detail. These polymers had melting temperatures below 220°C and were soluble in tetrahydrofuran and polar aprotic solvents that included dimethylformamide and dimethyl sulfoxide.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1981.170191131
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  • 122
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    Synthesis of polysulfone-amines by polyaddition of piperazines to divinyl sulfone (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 3031-3034 
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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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1981.170191135
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  • 123
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    Polycondensation reaction of dimethyl tartrate with hexamethylenediamine in the presence of various matrices (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 939-948 
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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 polycondensation reaction of dimethyl tartrate (DMT) with hexamethylenediamine (HMD) was carried out in dimethyl sulfoxide (DMSO) at 60°C in the presence of various polymer matrices, which were expected to interact with DMT or the resulting polyamide which had pendant hydroxyl groups due to hydrogen bonding. It was found that the rate of polycondensation was enhanced by polymer matrices such as poly(vinyl pyrrolidone) (PVP), Pullulan (polysaccharide) (PF), and poly(vinyl alcohol) (PVA). The rate enhancement became more pronounced with increasing molecular weight of the polymer matrix. When polycondensation in the presence of PVA was carried out in DMSO, a polymer complex was produced. The formation of the polymer complex between the resulting polyamide and PVA during polycondensation was dependent on the concentration of monomers and also on PVA; a gelation of the solution was observed at a concentration of PVA.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.170180315
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    Organosilane polymers. II. Poly(ethylmethyl-co-dimethylsilylene) and poly(methylpropyl-co-dimethylsilylene) (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 959-965 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polydimethylsilylene is a largely crystalline, high-melting polymer that is soluble only above 200°C and does not thermoform below its decomposition temperature. Introduction of ethyl and propyl substituents into the linear silylene system by random copolymerization of dimethylsilylene with ethylmethyl- and methylpropylsilylenes leads to tractable polymers that are soluble in common solvents at normal ambient temperatures.
    Additional Material: 7 Ill.
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    Functional monomers and polymers. LXIII. A study on the polymer-polymer interaction between nucleic acid base-substituted poly-L-lysinesFor Part LXII see ref. 1. (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 949-958 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study of polymer-polymer interaction was made on several poly-L-lysines that contained pendant nucleic acid bases substituted on the N′ position. Conformation and interaction of these polypeptides were studied in solution by spectroscopic measurement. The results obtained suggest that the high-molecular-weight polymers form polymer complexes in a helical conformation by specific adenine-thymine base pairing. On the other hand, no interaction could be observed for the low-molecular-weight polymers, which existed in a random coil structure.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.170180316
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  • 126
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    Polymer flammability. II (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 987-1009 
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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 responses of a polymer flame to changes of specimen diameter, ignition position, and stability of the burning surface were determined. These extrinsic flame parameters restricted the transport of oxygen from the environment to the burning surface. With increasing restriction the oxygen demand from the environment for self-sustained combustion increased from a minimum oxygen demand at maximum access of environmental oxygen to the burning surface. This increase in oxygen demand was measured and correlated with surface oxygen concentrations estimated from the diffusion data of Part I. The minimum oxygen demand was demonstrated as characteristic for a given polymer and intrinsic in its chemical structure. This minimum oxygen demand, termed intrinsic combustibility, has been correlated with a polymer's thermooxidative stability, measured by thermogravimetric analysis at specific conditions. An intrinsic combustibility scale for polymers is given. In contrast, polymer flammability, as commonly measured in air, is interpreted as a variable property that depends on the extent of the interaction between extrinsic parameters, which are set by the testing configuration, with intrinsic combustibility.
    Additional Material: 13 Ill.
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    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 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It was found 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.
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  • 128
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    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 
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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 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.
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    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 
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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: 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.
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    URL: http://dx.doi.org/10.1002/pol.1982.170200323
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    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 
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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 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.
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    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 
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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: 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.
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    Effect of initiation conditions on the direct polycondensation reaction using triphenyl phosphite and pyridine (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2745-2750 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In a model reaction of terephthalic acid with aniline by using triphenyl phosphite in a mixed solvent of pyridine and N-methylpyrrolidone (NMP), mono- and dianilides were produced with relative yields varying with the content of pyridine in the solvent. The polycondensation of terephthalic acid with aromatic diamines was found to proceed more favorably via monoamidation, and highmolecular-weight polyterephthalamides were prepared by controlling initiation conditions (selective activation of carboxylic groups), such as initial solvent systems, including the amount and kind of pyridines and initiation temperatures.
    Additional Material: 7 Tab.
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    Aromatic polyamides. I. Synthesis and characterization of some aromatic polyamides and their model diamides (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2799-2816 
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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 some wholly aromatic polyamides based on unsubstituted and chloro- and nitro-substituted diamines by low temperature solution polymerization is described. Poly(1,3-phenylene isophthalamide) and poly(chloro-2,4-phenylene isophthalamide) were selected for further investigation. To study the two polyamides on a systematic basis their model diamides were synthesized. These materials were characterized with respect to chemical structure and purity by elemental analysis, infrared (IR), and nuclear magnetic resonance (NMR) spectroscopic techniques. The usefulness of the model compounds in the interpretation of the polymer spectra is also demonstrated.
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    Synthesis of polyphthalimidines with benzylidene group from aminophthalide monomers (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2841-2845 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two aminophthalide monomers, 6-amino-3-benzylidenephthalide (I) and 3-(p-aminobenzylidene)phthalide (II), underwent self-polycondensation in o-phenylphenol at 250°C to yield polyphthalimidines with inherent viscosities up to 0.5 dL/g. These polymers were readily soluble in a variety of solvents such as dimethylformamide, dimethyl sulfoxide, m-cresol, pyridine, and methylene chloride. The temperatures at which a 10% weight loss occurred by thermogravimetry in nitrogen were 460°C for the polymer derived from I and 490°C for the polymer from II. The glass transition temperature of the polymer from I was 332°C, determined by thermomechanical analysis.
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    Synthesis and properties of poly(dimethylxylylenylamides) (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2895-2903 
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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(dimethylxylylenylamides) were synthesized from six different diphenylenediamenes and two dimethyl-substituted xylylenyldiacid chlorides by solution polycondensation at low temperature. The model compound 2,5-demethyl1,4-benzediacetanilide was synthesized and characterized by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy. The polyamides were characterized by IR and viscosity measurements. Some of the polyamides showed crystalline behavior in the x-ray diffractograms. The polyamdes have decomposition temperatures in the range 370-310°C in air and are soluble in all amide solvents. The effects of subsituents on crystallinity, thermal stability, and solubility of the polymides are also discussed.
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    Cationic polyelectrolytes. IV. Kinetic study of the reaction of acrylic polymers containing tertiary amine groups with halogenated compounds in dipolar aprotic solvents (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2881-2894 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction kinetics of halogenated compounds with tertiary amine groups attached at an acrylic macromolecular chain have ben studied. Three acrylic polymers were used. Two of them have mainly a structural unit of N, N-dimethylaminopropylacrylamide and the third is poly(N,N-dimethylaminoethylmethacrylate). Dimethylformamide, dimethylacetamide, and dimethylsulfoxide (DMSO) were used as dipolar aprotic solvents. Benzyl chloride and allyl chloride were considered as halogenated compounds with increased reactivity. The reaction kinetics depend on the polymer and halogenated-compound structures as well as the nature of the solvent. In the most of the cases the reactions carried out on polymers are accompanied by self-accelerating processes, with the exception of DMSO, which obviously has normal second-order kinetics. The reaction of polymers containing units of N,N-dimethylaminopropylacrylamide are compared with one having a low molecular weight, for instance N,N′-bis(3-dimethylaminopropyl)glutaramide.
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    4-Alkoxy-2-hydroxy-4′-vinylbenzophenones, ultraviolet-absorbing monomers (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2947-2953 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2,4-Dihydroxy-4′-vinylbenzophenone (I) and its 4-alkyl ethers (II), Me, Et, n-Bu, n-Oct, and n-dodecyl, were prepared in three steps by Hoesch synthesis, starting with p-(2-bromoethyl) benzonitrile and resorcinol and its monoalkyl ethers. I and its precursor 2,4-dihydroxy-4′-(2-bromoethyl) benzophenone were also converted into their 4-alkyl ethers with alkyl halides in dimethylformamide (DMF) in the presence of sodium hydrogen carbonate. Copolymerizations of I and II with styrene took place smoothly with satisfactory conversions to yield copolymers with ε-values around 104 L/mol cm-1 per benzophenone unit over the ultraviolet (UV) range of 235-340nm.
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    A 13C-NMR investigation of plasma polymerized ethane, ethylene, and acetylene (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2987-2996 
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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: Solid-state 13C-NMR spectra were obtained by cross-polarization and magic angle spinning of polymers prepared by injecting ethane, ethylene, and acetylene into a radiofrequency plasma. By use of the delayed decoupling technique to suppress protonated carbon peaks and difference spectroscopy five resolved spectral bands can be distinguished. These bands are assigned to (I) unsaturated nonprotonated, (II) unsaturated CH and CH2, (III) quaternary, (IV) methine and methylene, and (V) methyl carbons by comparison with standard 13C shifts compiled for organic materials. The relative amounts of these structural features in the polymers were determined quantitatively and the possible sources of errors considered.
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    URL: http://dx.doi.org/10.1002/pol.1981.170191130
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    Emulsifier-free emulsion polymerization with cationic comonomer (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 3013-3026 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An earlier article1 described the emulsion polymerization of styrene and various anionic comonomers, together with an anionic initiator, to give uniform latices at ca. 35% solids content. This article extends the work to cationic systems. Cationic comonomers 1,2-dimethyl 5-vinylpyridinium methylsulfate and 1-ethyl 2-methyl 5-vinylpyridinium bromide were synthesized and used with azobis(isobutyramidine hydrocholoride) initiator in the emulsifier- free emulsion polymerization of styrene. Recipes and results were generally comparable to those of the anionic systems, excepts for the dependence of particle diameter on comonomers concentration. Here the initial decrease was followed by an increase in particle diameter at higher comonomer content. The surface charge increased sharply with comonomer content.
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    ESR studies of some γ-irradiated organic crystals (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 3047-3061 
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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: Acrylamide, N-tert-butylacrylamide, and propionamide crystals were irradiated at -196°C and the structures of radicals studied by ESR spectroscopy at various temperatures. The γ-irradiated acrylamide crystals show a five-line spectrum which is similar in shape to the signal obtained from the γ-irradiated propionamide crystals. Two types of radicals are produced in irradiated acrylamide and propionamide crystals at -196°C. When the irradiated samples are kept at -78°C the spectrum of propionamide remains the same, except in intensity. In contrast to this, the acrylamide spectrum changes to a triplet because of dimerization. Upon warming the irradiated acrylamide sample to between -50 and -30°C, some small new peaks become apparent on either side of the triplet. These new peaks disappear above -20°C and the spectrum changes to a triplet because of polymerization. To observe the changes in the ESR spectra of γ-irradiated N-tert-butylacrylamide we kept the sample at various temperatures from -196 to 100°C. From -196°C to about room temperature the spectrum is a quintet. At and above 35°C, the spectrum changes to a triplet with shoulders on either side of the main peaks. With further warming above 80°C the spectrum changes to a broad triplet.
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    Surface reaction of particulate silica with polydimethylsiloxanes (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 3069-3079 
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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 interaction of silica and oligomeric methylsiloxanes, methylsilicone oil as well as silicone gum at elevated temperature was studied. It was found that a reaction takes place between surface silanols and octamethylcyclotrasiloxane (D4) above 180°C. Part of the methylsiloxane replaces the surface silanols forming loops with the surface, while the other part is redistributed to its neighboring homologoues. The methylsiloxy surface groups thus formed can undergo further reaction with the other methylsiloxanes above 250°C. Methylsilicone oil behaves similarly. The reaction with silicone gum was demonstrated by the formation of “chemically bound rubber.” The mechanism of the reaction is discussed.
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    A carbazole-based polymeric azodye (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 3155-3164 
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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 polymeric azodye has been synthesized from carbazole by diazotization of its derivative N-methylcarbazole-3,6-diamine and subsequent coupling reaction with 2,2-bis(4-hydroxyphenyl-3-sulfonate-Na)-propane prepared from bisphenol-A. Its physico-chemical, electrical, and thermal properties have been characterized; finally, its application to the preparation of colored semiconductive films from polyvinyl alcohol has been studied.
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    Thermal decomposition of polybutadienes by pyrolysis gas chromatography (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 3197-3208 
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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 thermal decomposition of cis-1,4-, trans-1,4-, and 1,2-polybutadienes (PBD) in the temperature range 450-900°C was investigated by pyrolysis gas chromatography (PGC). The cis- and trans-PBDs have closely similar product distribution and can be readily distinguished at lower temperatures of pyrolysis from the 1,2-PBD by the low amount of vinyl cyclohexene (VCH) produced by the 1,2 species. The amount of butadiene (BD) produced by 1,2-PBD varies with the tacticity of the polymer; the greater syndiotactic yields a lesser amount of BD. A method of determining the 1,4 and the 1,2 contents of PBD based on the ratios of peak heights of ethylene (C2) to VCH, propylene (C3) to VCH, and BD to VCH is presented. The advantages of this method are discussed. The nature and composition of the products of pyrolysis in the temperature range 540-900°C are presented and the mechanism of degradation at these elevated temperatures is explained.
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    Branching kinetics in copolymerization of styrene with a chain-transfer monomer (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 3209-3217 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In an earlier work it was shown that a random long-chain branching structure can be incorporated in polystyrene by copolymerizing styrene with a small amount of monomer that contains a chain transfer group. The use of vinylbenzylthiol as the chain transfer monomer produced a polystyrene with low number-average molecular weight and a degree of branching lower than expected. In this study polymerization kinetics were used to compute the theoretical molecular weight and degree of branching. The results show that if the chain-transfer constant of the chain transfer monomer is as high as that for vinylbenzylthiol the expected molecular weight and degree of branching will indeed be as low as those found experimentally. The theory also predicts that if the chain transfer constant is near one a highly branched bushy structure will result.
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    The preparation and reactions of polymeric azides. II. The preparation and reactions of various polymeric azides (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 3269-3284 
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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: Polymeric haloethyl acrylates, methacrylates, and methacrylamides, poly(vinyl chloride), poly-(epichlorohydrin), and halohydrins prepared from poly(glycidyl methacrylate), poly(butadiene), and poly(pentenamer) were converted to the corresponding azides. These azides reacted with a variety of acetylenic and olefinic derivatives to give, in most cases, good conversions to the corresponding triazole derivatives.
    Additional Material: 5 Tab.
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    Functional monomers and polymers. XCIVFor Part XCIII, see ref. 16.. Photochemical reactions on the synthetic polymers containing thymine bases in the presence of adenine derivatives (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 3315-3324 
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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: Photodimerization reactions of polyacrylate and polymethacrylate derivatives and the dimer model compound containing thymine bases were studied in the presence of adenine derivatives in dimethyl sulfoxide; N,N-dimethylformamide; and dimethyl sulfoxide-ethylene glycol solutions. The photodimerization of thymine bases both in the polymers and in the dimer model compound was found to be quenched by the addition of adenine derivatives. Base-base interaction in the ground state was also studied by ultraviolet (UV) spectroscopy in the three solvents. The quenching of the photodimerizationof thymine bases in the presence of adenine derivatives was discussed in terms of the specific interaction between adenine and thymine bases both in ground and excited states.
    Additional Material: 4 Ill.
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    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 
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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: 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.
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    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 
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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 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.
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    Evolution of aromatic compounds in the thermal decomposition of vinyl polymers (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1147-1153 
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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 thermal decomposition products that evolve from poly(vinyl chloride) (PVC), poly(vinylbromide) (PVB), poly(vinyl alcohol) (PVA), and poly(vinylacetate) (PVAc) were analyzed by direct pyrolysis in the ion source of a mass spectrometer (MS). Our results indicate that in both stages of the decomposition process which occurred in the four vinyl polymers investigated several aromatic hydrocarbons were produced and that the relative amounts of benzene, napthalene, and anthracene were different in the two stages. This previously unreported information determines in a single scheme the thermal behavior of the title compounds.
    Additional Material: 6 Ill.
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    Utilisation du dicyclohéxyl-18 couronne-6 en polymérisation anionique. II. Polymérisation du methacrylate de methyle amorcee par les metaux alcalins (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1155-1161 
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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 purpose of the present work, relative to anionic polymerization, is to describe the use of DCHE in order to prepare stable alkali metal solutions in low-dielectric-constant solvents. All these new species initiate the polymerization of methyl methacrylate avoiding the inconvenience of heterogeneous reactions. The presence of complexed ion pairs increases the syndiotactic structure. The polymerization seems to obey the Bernoullian statistics.
    Additional Material: 1 Ill.
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    Polymérisation anionique de i'isoprene et du butadiene en presence d'agents complexants (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1163-1169 
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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: With the aid of DCHE and [222], solutions of sodium, potassium, rubidium, and cesium have been prepared in tetrahydrofuran (THF) and in benzene. All these new species initiate the polymerization of butadiene and isoprene avoiding the inconvenience of heterogeneous reactions. The presence of free ions and/or complexed ion pairs allows the increase of vinyl structures even in benzene.
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    Grafting onto wool. IV. Effect of amines upon ceric ion-initiated grafting of poly(methyl acrylate) (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1171-1176 
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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: Grafting of poly(methyl acrylate) onto wool has been carried out in an aqueous medium at 45 ± 1°C by using ceric ammonium nitrate (CAN) in the presence of triethylamine, diethylamine, n-butylamine, triethanolamine, and N,N-dimethylaniline. The percentage of grafting varied with the nature and concentrations of the amines. Reactivity of the different amines toward grafting reactions followed the order: triethylamine 〉 diethylamine 〉 n-butylamine 〉 triethanolamine ≥ N,N-dimethylaniline. In the presence of N,N-dimethylaniline grafting did not occur. An attempt has been made to explain the observed reactivity of Ce4+ in various amine systems in graft copolymerization reactions.
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    Determination of initiation rate of copolymerization of acrylonitrile with p-bromophenyl acrylate carried out in N,N-dimethylformamide (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1177-1187 
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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 initiation rate of the copolymerization reaction of acrylonitrile with p-bromophenyl acrylate initiated by azobisisobutyronitrile in dimethylformamide at 60°C are reported. The inhibition method involved use of stable Banfield's radical (N-[1,1-dimethyl 3-(N-oxidophenylimine)butyl]-N-phenylaminyl oxide). In the case of acrylonitrile, a side reaction effect of the initiation with the stable radical was observed along with a retarding effect resulting from inhibition reaction products (2kdf)60AN = 8.2 × 10-4 min-1. During the inhibited homopolymerization of p-bromophenyl acrylate a very strong side initiation reaction effect results from the Banfield radical; the inhibition reaction products do not influence the further course of the polymerization reaction. Side initiation effects of the Banfield radical (BR) increase with increasing concentration of p-bromophenyl acrylate. The overall contribution of the side initiation reaction changes for different comonomer mixtures; with their compositions the actual changes are nonadditive. The inhibition reaction products do not influence the further course of copolymerization. The initiation rate in monomer mixtures depends on their composition and may be described by the following relation: $$ 2k_d f = (2k_d f)_{{\rm AN}} \times X_{{\rm AN}}^{1.1} + (2k_d f)_{{\rm pBrPhA}} \times X_{{\rm pBrPhA}}^{1.7} $$
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    Model for predicting the composition of copolyesters: Polymerization of terephthalic acid, 2,2′-oxydiethanol, and 2,2-dimethyl-1,3-propanediol (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1189-1202 
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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: Copolyesters of two glycols and a dicarboxylic acid moiety are frequently made to obtain specific physical properties. In the synthesis of these polymers an excess of glycol is used in the ester-exchange reaction and then removed during the polycondensation reaction to form a high-molecular-weight product. A model has been developed to predict the final polymer composition. The derivation is based on equilibria of reaction species (free glycol, polymer chain ends, and ester links) and the relative vapor pressures of the two reacting glycols. Calculated results are compared with experimental results of poly(2,2′-oxydiethylene: 2,2-dimethyl-1,3-propylene terephthalate)s. There is good agreement between calculated and experimental compositions. The model can be used to calculate the glycol concentrations that must be used to make a specific polymer composition. This model should also be useful in the calculation of other mole ratios of glycol to dicarboxylic acid that will make the same composition.
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    Amylose-polyester block copolymers (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 997-1009 
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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 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.
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    Thermal-induced conversion of maleic and fumaric acid anion radicals in poly(methyl methacrylate) (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1213-1221 
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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: Thermal-induced conversion of maleic and fumaric acid anion radicals produced by γ irradiation at 77 K in poly(methyl methacrylate) (PMMA) was studied by electron spin resonance (ESR) and optical absorption spectroscopic measurements. The ESR spectra of these acid anion radicals change into two-line spectra with a line separation of ca. 10 G by thermal annealing. This spectrum is assigned to a protonated radical of each acid anion radical. Anion radicals of the solutes are relatively stable below the γ transition point of PMMA and the conversion reaction takes place near this point. This means that the molecular motion of matrix molecule affects the radical conversion reaction.
    Additional Material: 8 Ill.
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    Kinetics of radical polymerization. XXX. Polymerization of styrene in solution (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1223-1232 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study was made on the AIBN-initiated polymerization of styrene in benzene and dimethyl formamide at 50°C. The overall rate and the rate of initiation of the polymerization were determined and the number-average and weight-average molecular weights of the polymers formed were measured. The decrease in the rate and degree of polymerization with the decrease in styrene concentration was caused by the corresponding decreases in the rate constants of chain propagation and initiation steps. In the systems studied no chain transfer process occurred with an experimentally measurable rate.
    Additional Material: 7 Ill.
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    An investigation of the vacuum UV spectra of inductivity coupled RF plasmas excited in inert gases as a function of some of the operating parameters (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1233-1246 
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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 vacuum ultraviolet (UV) emission from inductively coupled radio-frequency (RF) plasmas excited in a series of inert gases has been studied as a function of the pressure and applied power of the system. The effects of discharge tube size and pulsing of the applied RF power are also considered and a comparison is made between RF and microwave excitation.
    Additional Material: 9 Ill.
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    Syntheses of polyethylenimine containing asymmetric nucleic acid base derivatives as grafted pendants (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1247-1265 
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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: Preparations of new model polymers of polynucleotides with linear polyethylenimine (PEI) backbones and optically active nucleic acid base derivatives as pending side chains are described. (±)-2-(Thymin-1-yl)propionic acid (II) and (±)-2-(adenin-9-yl)propionic acid (IV) were synthesized. These carboxylic acid derivatives were grafted onto PEI at the imino nitrogen by the p-nitrophenyl active ester method. The enantiomeric pairs of II were optically resolved with quinine to yield (-) and (+)-2-(thymin-1-yl)propionic acid (VII and VIII). VII and VIII were grafted onto PEI through amide bond by direct coupling with diethylphosphoryl cyanide to give optically active graft polymers. The related monomer and dimer model compounds were also prepared by the same method from diethylamine and dimethylethylene diamine, respectively.
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    Circular dichroism of polyethylenimine containing optically active thymine derivatives as grafted pendants (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1267-1277 
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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: Optical properties of linear polyethylenimine containing optically active (+)- or (-)-2-(thymin-1-yl)propionyl group as grafted pendant were investigated by circular dichroism (CD) and compared with those of the related monomer and dimer model compounds. CD spectra of the polymer in neutral aqueous solution were different from those of related model compounds, which suggest that the polymer exists in some ordered conformation (at least locally) to allow exciton coupling of π-π* (B2u) transition in the base chromophores along the polymer chain. This ordered conformation tends to be randomized on heating. The effects of complementary base pairing on the CD spectra have also been studied by using a linear polyethylenimine containing (±)-2-(adenin-9-yl) propionyl grafts and its related monomer and dimer models.
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    Determination of sulfate and similar end groups in polymers [poly(methyl methacrylate) and polystyrene] by an improved dye interaction method (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1279-1284 
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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 has been observed that in a benzene medium the carbinol base of a cationic dye reacts with a polymer with —SO3 Na and similar end groups that give rise to a reversible color formation of the dye cation. This reaction can be pushed to completion and consequent intensification of color by adding a benzene-insoluble acid such as citric acid. This principle has been applied to develop an improved dye interaction method of determining such end groups. The end groups values thus obtained by this method for different poly(methyl methacrylate) and polystyrene samples were found to be in fairly good agreement with those obtained by the dye partition (extrapolation) method.
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    Molecular weight distribution in emulsion polymerizations (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1297-1323 
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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 mathematical formulation is given which describes the evolution of the number distribution of the molecular weight (MWD) of linear polymer chains that grow in emulsion polymerization systems. The resulting set of coupled ordinary differential equations takes into account the microscopic events of free radical entry, exit, chain annihilation, bimolecular termination (by combination and disproportionation), and chain transfer in a mono- or polydisperse system. Simple analytic solutions are presented for systems in which the number of particles, as well as the average number of free radicals per particle, is constant and in which the rate coefficients are size independent. These solutions indicate that compartmentalization of the free radicals in the latex particles results in a significant increase in the polydispersity of the polymer produced by emulsion polymerization, compared with that in bulk systems. The theory shows that significant mechanistic information may be obtained from experimental MWDs and that, in principle, experimental conditions may be prescribed to grow a desired MWD. The MWDs are presented in a novel manner that facilitates the comparison of theory with experiment.
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    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 
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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 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.
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    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 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of poly(vinyl alcohol) 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.
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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 
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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 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.
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    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.
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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.
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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 
    Details
    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.
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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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    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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  • 171
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    Effect of solvent on the copolymerization of ethylene and vinyl acetate (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1347-1357 
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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 ethylene (M1)-vinyl acetate (M2) copolymerization at 62°C and 35 kg/cm2 with α,α′-azo-bisisobutyronitrile as initiator has been studied in four different solvents, viz., tert-butyl alcohol, isopropyl alcohol, benzene, and N,N-dimethylformamide. The experimental method used was based on frequent measurement of the composition of the reaction mixture throughout the copolymerization reaction by means of quantitative gas chromatographic analysis. Highly accurate monomer reactivity ratios have been calculated by means of the curve-fitting I procedure. The observed dependence of the r values on the nature of the solvent is surprisingly large and can be correlated with the volume changes (= excess volumes) observed on mixing vinyl acetate (VAc) with the relevant solvent. An increased hydrogen bonding or dipole-dipole interaction through the carbonyl moiety of the acetate side group of VAc, induces a decreased electron density on the vinyl group of VAc, which in turn leads to a decreased VAc reactivity. The differences among the overall rates of copolymerization in the various solvents can be interpreted in terms of a variable chain transfer to solvent and the rate of the subsequent reinitiation by the solvent radical. In the case of benzene, complex formation is believed to play an important part.
    Additional Material: 6 Ill.
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    Effect of polyion conformation on dye binding. V. Induced optical activity of acridine orange bound to a synthetic nonstereoregular polyelectrolyte (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1367-1373 
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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 shown that the induced Cotton effects in the visible region of the absorption bands of acridine orange in the presence of a nonstereoregular α-carboxylic polysulfonamide (PLL) can be attributed to stacked bound dye molecules, irrespective of the conformation of the polymer. The existence of an ordered structure seems to be unnecessary for such an induction.
    Additional Material: 4 Ill.
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  • 173
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    Structure of aromatic polyimides (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1375-1385 
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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: With a view to understanding the structure of aromatic polyimide backbone, model compound N,N-bis(4-phenoxyphenyl)-1,2:4,5-benzenetetracarboxdiimide was synthesized by the condensation of pyromellitic dianhydride and 4-aminodiphenyl ether in solvent N,N-dimethylacetamide or N,N-dimethylformamide. Various side products formed during the reaction were isolated and identified by spectroscopical methods. This study reveals that the polymer backbone contains nearly 85% imide rings. The uncyclizable residues in the backbone are those derived by the chemical interaction of polymerization solvent or by the modification of intermediate orthoamido acid. The uncyclizable nature of the latter was explained in mass and infrared (IR) spectral studies. The role of the dipolar solvent appears to be vital to imidization.
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    Organometallic polymers. VI. Anchoring of arenechromium carbonyl complexes to macroreticular polymersFor Part V see ref. 1. (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1387-1397 
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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 phenanthrenechromium dicarbonyl moiety was anchored by a photosubstitution reaction onto commercial resins substituted by diphenylphosphine groups. From scanning electron microscope photographs it was found that, whereas the chloromethylation reaction proceeded homogeneously throughout the polymer beads, the phosphination and photochemical reactions behaved differently, depending on the macrostructure and the morphology of the polymer beads. Large pore size dimensions (1300 Å) allowed the reagents (phosphine and chromium complex) to react throughout the polymer beads, whereas small pore sizes (〈 50 Å) permitted penetration of the reagent only to a limited extent.
    Additional Material: 9 Ill.
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    The study of macronet isoporous styrene polymers by gel permeation chromatography (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1399-1406 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Gel permeation chromatography was used for studying the structure of macronet isoporous styrene polymers swollen in chloroform. The polymers were obtained by crosslinking polystyrene either in a solution or in a swollen state using monochlorodimethyl ether and p-xylylenedichloride via the Friedel-Crafts reaction. It is shown that the networks obtained by structurization of concentrated polystyrene solution in a good solvent are characterized by loose structure, fine pores (ca. 10 Å), and narrow pore distribution. In poor solvents or in strong dilution of polystyrene and at the instant of net formation, the polymers that are obtained contain, in addition to fine pores, large pores with diameters up to 300 Å.
    Additional Material: 4 Ill.
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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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    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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    Evaluation of monomer reactivity ratios of more complex copolymerization schemes, with application to the penultimate unit effect in methyl acrylate-butadiene copolymerization (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1431-1431 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.170180426
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    Synthesis and optical properties of polyethylenimine containing L-proline and optically active thymine derivatives (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1433-1446 
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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: Preparation and optical properties of linear polyethylenimine (PEI) containing L-(-)-N-[(-)-2-(thymin-1-yl) propionyl] prolyl group as grafting pendant, [P-(-)Pro-(-)T], and its related monomer and dimer model compounds are described. Hypochromic effects and circular dichroism of these compounds were compared with those of PEI containing (-)-2-(thymin-1-yl) propionyl group as grafting pendant, [P-(-)T], which has no L-proline ring as a spacing group. P-(-)Pro-(-)T showed no exciton coupling of B2u π-π* transition although it showed large hypochromicity in neutral aqueous solution, implying that the stacking of the bases has no screw sense.
    Additional Material: 8 Ill.
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    Graft copolymerization onto jute fiber: Ceric ion-initiated graft copolymerization of methyl methacrylate (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1447-1458 
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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: Graft copolymerization of methyl methacrylate (MMA) was carried out on both defatted and bleached jute fibers using ceric ammonium sulfate (CAS) as the initiator. In order to obtain the optimum condition for grafting, the effects of initiator concentrations, temperature, time of reaction, lignin content of jute, and the monomer concentration were studied. The maximum percent grafting and grafting efficiency were found to be 132% and 0.71, respectively. Kinetic studies showed that at 0.03M CAS, the reaction appeared to obey the second-order process. The activation energies were found to be 7.74 and 5.12 kcal/mole for defatted (lignin content, 15.7%) and chlorite-bleached jute (lignin content 10%), respectively. The activation energies of graft copolymerization of MMA onto jute fiber are compared with the energies of activation of graft copolymerization of acrylonitrile (AN).
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    Electrochemical and chemical polymerization of acrylamide (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1459-1469 
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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 electrochemical and chemical polymerization of acrylamide (AA) has been studied. The electrolysis of the monomer in N,N-dimethylformamide (DMF) containing (C4H9)4NClO4 as the supporting electrolyte leads to polymer formation in both anode and cathode compartments. The cathodic polymer dissolves in the reaction mixture and the anodic polymer precipitates during the course of polymerization. A plausible mechanism for the anodic and cathodic initiation reaction has been given. The chemical polymerization of acrylamide that has been initiated by HClO4 is analogous to its anodic polymerization. The polymer yield increases with an increase in concentration of the monomer and HClO4. Raising the reaction temperature also enhances the polymerization rate. The overall apparent activation energy of the polymerization was determined to be ca. 19 kcal/mole. The copolymerization of acrylamide was carried out with methyl methacrylate (MMA) in a solution of HClO4 in DMF. The reactivity ratios are r1 (AA) = 0.25 and r2 = 2.50. The polymerization with HClO4 appears to be by a free radical mechanism. When the polymerization of acrylamide is carried out with HClO4 in H2O, a crosslinked water-insoluble gel formation takes place.
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    Evolution of HCN by thermal oxidative degradation from nylon 66 at high temperatures including burning (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1471-1481 
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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: Work on the evolution of HCN from nylon 66 was extended to temperatures from ca. 300 to 695°C. Below ca. 300°C the evolution of HCN is governed by chemical decomposition, and above 300°C the evolution is controlled by diffusion. Above 530°C oxidation of HCN becomes noticeable and ignition occurs at 590°C. The rate constants for all of the temperature ranges and for the oxidation of HCN are given in terms of Arrhenius equations. The activation energy for the oxidation of HCN before ignition (590°C) is reached is 47 kcal/mole, and beyond this point, the oxidation is controlled by diffusion. The rate constants increase linearly with oxygen concentration as long as HCN oxidation is negligible; however, they pass through maxima if HCN oxidation is appreciable (some HCN is evolved even in the absence of oxygen). A new flash degradation apparatus has been constructed for these high-temperature ranges and a degradation mechanism has been proposed which is in satisfactory agreement with the experimental results.
    Additional Material: 11 Ill.
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    The effect of tin stabilizers on the thermal degradation of poly(vinyl chloride) (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1483-1488 
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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: Simultaneous HCl evolution and spin-generation measurements were made on poly(vinyl chloride) (PVC) samples containing stabilizers of the type Rx Sn Y4-x. It was found that tetrabutyltin and tributyltin laurate were better stabilizers than dibutyltin dilaurate. On the basis of the results, a mechanism for the stabilization of PVC by this class of compounds is proposed.
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    Stereochemistry in cationic polymerization of alkenyl ethers. V. Stereochemistry of acetal additions as model reactions for the polymerization of alkenyl ethers (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1489-1498 
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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: Acetal additions to β-substituted vinyl ethers having a variety of substituents (alkenyl ethers) were stereochemically investigated as model reactions for their cationic polymerization. The reactions catalyzed by BF3O(C2H5)2 in CH2Cl2 at O°C gave 1:1 adducts, the steric structure of which was determined by means of 13C-NMR spectroscopy. trans-Alkenyl ethers always gave adducts with a single structure stereospecifically, indicating that the intermediate carbocation attacks a trans-alkenyl ether from a definite direction independent of the bulkiness of substituents. On the other hand, cis-alkenyl ethers formed adducts with two steric structures, and the direction of cation addition was found to depend on the bulkiness of the alkoxy group involved. The above trends were in agreement with the results for poly(alkenyl ether)s and allowed detailed discussion of the stereochemistry of the propagation processes in alkenyl ether polymerizations.
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    Reaction of crotonaldehyde with various ethyl aluminum chlorides in methylene chloride. A 1H-NMR study (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1499-1509 
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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 reactions of crotonaldehyde (CA) with ethyl aluminum chlorides have been examined using a titration technique at low temperature. The titrations were followed by 1H-NMR spectroscopy. Evidence for complexes of the type (Et2AlCl)2CA and (Et2AlCl-CA)2 has been obtained. Ethyl aluminum sesquichloride undergoes sequential addition of CA to the EtAlCl2 moiety, to the Et2AlCl moiety, and again to the EtAlCl2 moiety. Ethyl aluminum dichloride undergoes ligand redistribution, alternately disproportionating and reproportionating, the ultimate product being EtAlCl2-CA2.
    Additional Material: 8 Ill.
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    New processable poly(ether-keto-sulfone)s, poly(arylene sulfone)s, and polyesters curable by intramolecular cyclization. XVII (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1511-1521 
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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: New processable polyaromatic ether-keto-sulfones were prepared from 2,2′-diiododiphenyl-4,4′-dicarbonyl dichloride (I), bis(p-phenoxybenzene)sulfone (V), isophthaloyl chloride (VI), terephthaloyl chloride (VII), and diphenylether (IX) in Friedel-Crafts-type polymerizations. By varying (VI):(VII) ratio and (V):(IX) ratio and by reducing the polymerization time, soluble, processable polymers were obtained. In these polymers, phenylacetylenyl groups were introduced by replacing the iodine. This process led to soluble and curable polymers. Transparent, tough films and fairly flexible glass fiber laminates can readily be prepared. After curing, the polymers were insoluble and showed excellent chemical and thermal resistance. The curing process increased the polymers' softening temperature by ca. 20°C and produced intersting new useful materials for laminates. Processable poly(arylene sulfone)s were prepared from I, V, and diphenylether-4,4′-disulfonylchloride (X) in a Friedel-Crafts-type polymerization. Different monomer ratios and polymerization times were used. Only low-molecular-weight polymers were obtained. The same result was shown by curable polyester formation from I, VI, VII, and 4,4′-sulfonyldiphenol (XI) in an interfacial polycondensation.
    Additional Material: 6 Tab.
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    New telechelic polymers and sequential copolymers by polyfunctional initiator-transfer agents (inifers). II. Synthesis and characterization of α,ω-di(tert-chloro)polyisobutylenes (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1523-1537 
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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: Detailed understanding of the mechanism of initiation and chain transfer in BCl3-coinitiated isobutylene polymerization led to the efficient synthesis of symmetric telechelic polyisobutylenes carrying ∼CH2C(CH3)2Cl groups at either end of the molecule Cl-PIB-Cl. The synthesis is based on the use of inifers, i.e., bifunctional initiator-transfer agents that effect controlled initiation and propagation in the absence of chain transfer to a monomer. Specifically, the synthesis of Cl-PIB-Cl was achieved by the p-dicumyl chloride/BCl3/isobutylene/CH2Cl2 system. According to the inifer mechanism each Cl-PIB-Cl contains two terminal tertiary chlorines and one phenyl group at the interior of the chains. The structure of this new symmetric telechelic polymer has been established by detailed characterization studies including a sensitive new gel permeation chromatography (UV plus RI) analysis method, 1H-NMR, kinetic experiments, and chemical derivatization. The Cl-PIB-Cl molecule is a key intermediate for the synthesis of hosts of new materials, e.g., triblock copolymers, α,ω-diolefins, and α,ω-difunctional polymers.
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    Polymerization of N-vinylpyrrols (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1547-1550 
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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: The free polymerization of 2-methyl-1-vinylpyrrol (I), 2,3-dimethyl-1-vinylpyrrol (II), 1-vinyl-4,5,6,7-tetrahydroindol (III), 1-vinyl-2-phenylpyrrol (IV), and 1-vinyl-2-phenyl-5-trifluoroacetyl pyrrol (V) in the presence of azobisisobutyronitrile as an initiator at 60-80°C has been studied. The polymer yield (up to 90%) and molecular weight in the range 2000-13,000 are strongly dependent on the monomer structure and the polymerization conditions. The reactivity of N-vinylpyrrols studied falls in the order: I 〉 III 〉 II 〉 V 〉 IV implying an important role of the initial radical stabilization with the participation of the ring substituents as well as the steric hindrances in the propagation stage.
    Additional Material: 2 Tab.
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    URL: http://dx.doi.org/10.1002/pol.1980.170180511
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    New telechelic polymers and sequential copolymers by polyfunctional initiator-transfer agents (inifers). III. Synthesis and characterization of poly(α-methylstyrene-b-isobutylene-b-α-methylstyrene) (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1539-1546 
    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 a new glassy-rubbery-glassy triblock copolymer poly(α-methylstyrene-b-isobutylene-b-α-methylstyrene) has been demonstrated. The key to the synthesis was the preparation by inifer method of a perfectly bifunctional polyisobutylene which carries tert-chlorine end groups Cl-PIB-Cl. In conjunction with Et2AlCl coinitiator, the telechelic Cl-PIB-Cl molecule initiates the polymerization of α-methylstyrene at both ends of the prepolymer. Triblock composition can be controlled by the judicious selection of synthesis conditions; that is, Cl-PIB-Cl molecular weight, α-methylstyrene concentration, and solvent polarity. Theoretical triblock Mn calculated from Mn of Cl-PIB-Cl and triblock overall composition is in excellent agreement with experimental Mn which indicates negligible homopolymer contamination. Extraction with a series of hydrocarbon solvents reveals broad composition distribution. The stress-strain profile of a triblock is similar to that of a poly(styrene-b-butadiene-b-styrene) thermoplastic elastomer of similar composition.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.170180510
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  • 190
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    Monte Carlo-studium der reversiblen copolymerisation. I. Theorie, memøry-6 programm, anwendungen (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1559-1564 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The binary reversible copolymerization, taking into account the length of the terminal sequence, are studied by the Monte Carlo method. We discuss the theoretical model, the algorithm, and a FR̃RAN program. Finally, the α-methylstyrene-methyl methacrylate copolymerization is studied by means of the proposed Monte Carlo model, and the results obtained are compared with those obtained using the Markov chain model and Wittmer's equations.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.170180513
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  • 191
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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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  • 192
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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.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    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 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/pol.1982.170200724
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  • 194
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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 
    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.1982.170200731
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  • 195
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    Polymer effect in graft polymerizations of acrolein onto imidazole-containing polymer (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1599-1608 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The graft polymerizations of acrolein (AL) onto an imidazole (Im)-containing polymer, such as a homopolymer of 4(5)-vinylimidazole (VIm) and several copolymers of VIm-4-vinylpyridine (VPy), VIm-1-vinyl-2-pyrrolidone (VPr), and VIm-styrene (St), have been studied in ethanol at 0°C. The degree of polymerization (P̄n) of the resulting polyacrolein graft depended on the number of Im units in the Im-containing polymer which produced a decrease in P̄n of grafted polyacrolein. The P̄n of the graft polyacrolein was determined to be in the range of 5-23. The rate of polymerization (Rp) was expressed by Rp = k(PVIm) (AL)2. The graft polymerizability of the AL was influenced by the comonomer in the parent polymer, and was found to be in the order of VIm homopolymer 〉 VIm-VPr copolymer 〉 VIm-VPy copolymer 〉 VIm-St copolymer. Rp was affected by the functional group around the Im group in the Im-containing polymer. These results were discussed by assuming the conformation of the parent polymer in ethanol.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.170180517
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    A novel synthesis of α-d-acrylonitrile (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1609-1610 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.170180518
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    ESR signal of polymer prepared In Situ in xylene plasma (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1611-1613 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.170180519
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    The synthesis and reactions of polysulfites derived from 2,2-bis(4-hydroxyphenyl)propane (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1615-1617 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.170180520
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  • 199
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    Nitration-nitrosation of methyl methacrylate in the presence of nitric-acid (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1619-1626 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.170180521
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    Triphenylphosphine termination of tetrahydrofuran polymerization in the presence of silver salts (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1627-1632 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.170180522
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