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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1-11 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dispersion polymerization of styrene in the particle size range of 10 μ with lauroyl peroxide as initiator results in a double-peak molecular weight (MW) distribution. The high-MW fraction was due to emulsion polymerization. The same phenomenon also exists in AIBN and benzoyl peroxide initiation, although it is less obvious. The kinetics of the reaction for dispersion polymerization was dependent on the concentration of the dispersing agent and the nature of the initiator.
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  • 2
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The plasma polymers formed in glow and nonglow regions of an inductively coupled RF plasma with perfluorobenzene and perfluorocyclohexane are discussed as a function of operating conditions of the plasma by means of ESCA. The core levels of the plasma polymers are shown to be strikingly different but characteristic of a well-defined but complex polymerization scheme. For the nonglow regions fluorine incorporation is shown to be greater than for polymers prepared in the glow regions and a preponderance of CF2 features is apparent. Perfluorobenzene deposits polymer faster than perfluorocyclohexane and changes in component composition of the C1s profile are studied as a function of operating conditions of the gas plasma.
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  • 3
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: MoCl5, WCl6, and OMoCl4 were found to be effective initiators for the polymerization of acetylene and its monosubstituted derivatives RC=CH. The polymerization proceeded in homogeneous and heterogeneous media and was carried out in nonpolar (chloroalkanes, aromatic hydrocarbons) and polar (THF, acetone, dioxane, carboxylic acids) solvents to give a high yield of polymers.
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  • 4
    Electronic Resource
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 47-51 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this investigation an approach to correlate the composite rate constants of some redox polymerization reactions [acrylonitrile-Ce(IV)-organic substrate] with a new type of multiparameter equation is described. The multiparameter equation is based on Swain and Lupton's F and R, the field and resonance components of the substituents, respectively, and the unique positional weighting factors f and r suggested by Williams and Norrington. The statistical parameters of the correlation involving the substituent constants (fF and rR) and the rate data have been found to be quite satisfactory, the average coefficient of determination being 0.91. The significance levels of the correlation also indicate that the present model is applicable to the kinetics of redox polymerization. The sign and magnitude of the reaction-dependent regression constants α and β suggest that three different types of reaction mechanisms are operative for the substrates benzaldehyde, phenylthiourea, acetophenone, and toluene.
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  • 5
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four solvents of cellulose have been studied by using 13C-NMR spectroscopy. All these solvents, N-methyl morpholine-N-oxide, methylamine, hydrazine, and paraformaldehyde (PF), contained dimethyl sulfoxide (DMSO) as a cosolvent. Oligomers of cellulose of DP = 10 soluble in hot DMSO have been used as model compounds. 13C chemical shifts and line shapes show that three of the mentioned solvents are “true solvents” of cellulose. On the other hand, dissolution of cellulose in DMSO-PF system occurs by the formation of a statistical derivative of cellulose. Enriched 13C bacterial cellulose on C-1 and C-6 positions have been used to identify the 13C positions mainly in DMSO-N-methyl morpholine-N-oxide system. This solvent has been found to be degradative for the macromolecule when the solution is kept at 100°C over a long period. Viscosity measurements show a reduction of the molecular weight in these conditions. Polarimetry indicates that no glucose is present in solution and hence there is a statistical break of the chain. Enriched cellulose solution in DMSO-N-methyl morpholine-N-oxide has been also used for relaxation time (T1) determination both of the solvent and of the enriched carbons of the polymer. Nuclear Overhauser enhancement (NOE) was found to be 1.8 for C-1 and 2.1 for C-6 showing that relaxation phenomenon is not purely dipolar. T1 values of 97 and 65 msec are found for C-1 and C-6 of cellulose, in good agreement with the values known for polysaccharides. Determination of T1 for the different carbon atoms of the solvent DMSO-N-methyl morpholine-N-oxide with and without cellulose shows a large reduction of T1 for N-methyl morpholine-N-oxide molecule. This denotes a slower molecular motion of this molecule and a preferential interaction with the cellulose macromolecule.
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  • 6
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 109-121 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vinyl fluoride was polymerized by photochemical initiation in a continuous-flow cylindrical reactor at room temperature and at pressures of up to 30 atm. Copolymers with vinyl acetate were prepared in order to improve the solubility and processability of poly(vinyl fluoride) (PVF). The copolymers were hydrolyzed to the corresponding vinyl alcohol copolymers and yielded hydrophilic films that are strong and flexible only when swollen by water. It was found that on hydrolysis the Tg, Tm, and heat of fusion as well as degree of crystallinity increased. It was suggested that PVF and the copolymers with vinyl alcohol are isomorphous.
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  • 7
    Electronic Resource
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 147-155 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Solution and solid-state thermal cis-trans isomerization of cis-transoidal polyphenylacetylene was investigated. At temperatures higher than 120°C, cis-trans thermal isomerization in solution is accompanied by cyclization, aromatization, and scission of the polymer chain. Both spectral and kinetics data showed that at temperatures lower than 120°C, not only cis-trans thermal isomerization takes place but also intramolecular cyclization.
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  • 8
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 157-168 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Direct fluorination of the hexafluoroacetone-ethylene copolymer, [CH2CH2OC(CF3)2]n, under conditions designed to promote fragmentation of the polymer chain has led to the synthesis of a number of structurally unusual branched perfluoropolyethers [—CF2—CF2—O-C(CF3)2—]n. These new perfluoropolyethers have been characterized by 19F-NMR, and their physical properties are reported. Direct fluorination under milder conditions yields a high-molecular-weight perfluoropolyether.
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  • 9
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 179-189 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bulk polymerization of isobutyl vinyl ether was studied at 25°C in a wide dose rate range, 8.2-277 rad/sec by γ rays and 8.8 × 103-2.2 × 105 rad/sec by electron beams. At low dose rate, 8.2-277 rad/sec, only the radical polymerization took place. At high dose rate exceeding 8.8 × 103 rad/sec, cationic polymerization was found to occur in addition to the radical polymerization. DPn of the product at high dose rate was 9-10. Further drying of the monomer increased Rp, and molecular weight of the product formed by cationic mechanism also increased.
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  • 10
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 169-178 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radiation degradation behavior of methyl α-chloroacrylate (MCA) and methacrylonitrile (MCN) copolymers has been investigated as part of a program to develop high-sensitivity polymeric resists for integrated circuit manufacture. High-molecular-weight copolymers were prepared by emulsion techniques. Several different copolymer compositions were prepared varying from 19 to 68 mole % MCA. These copolymers were fractionated and then subjected to γ irradiation from a 60Co Source. The Gs - Gs, Gs - 4Gs values were determined from M̄;F〉nk-1 and Gu-1 versus dose plots, and the Gfs and Gs Values were then calculated. Molecular weights of both unirradiated and irradiated polymers were analyzed by membrane osmometry and gel permeation chromatography. All copolymers exhibited higher degradation susceptibilities than that of poly(methyl methacrylate) (PPMA), which has Gx = 1.3. The individual Gx and Gx values of the copolymers were found to fall between those of the two homopolymers, poly(methyl α-chloroacrylate) (Gx = 6.0) and polymethacrylonitrile (Gx ∼ 3.1). The dependence of Gx and Gx values on molecular weight was minor. The crosslinking susceptibility of the poly(methyl α-chloroacrylate) (Gx ∼ 0.8), was greatly decreased by copolymerization with MCN. Relatively small amounts of MCN caused a large drop in Gx, i.e., Gx ∼ 0.15 at 32% MCN and Gx ∼ 0.03 at 51% MCN. The observation could be attributed to the decreasing probability that crosslinking sites, in the MCA monomer units on adjacent chains, would lie in close proximity.
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  • 11
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 191-202 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bulk polymerization of α-methylstyrene was carried out in a wide dose rate range, 7.6-256 rad/sec by γ rays and 8.5 × 103-2.1 × 105 rad/sec by electron beams. At high dose rate by electron beams, cationic polymerization took place along with formation of oligomeric product of DPn = ∼4. At low dose rate by γ rays, radical polymerization was found to occur in water-saturated monomer. The cationic polymerization at high dose rate proceeds with essentially the same mechanism as was already known in γ-ray polymerization of dry monomers. Relatively low reaction rate of the cationic polymerization compared with that of styrene is explained with the fact that the propagation of α-methylstyrene is much more easily inhibited by a slight amount of water.
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  • 12
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 223-233 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New polymeric cinchona alkaloids having favorable structures and properties for asymmetric catalysts have been prepared by radical copolymerization of the alkaloids with acrylonitrile using azobisisobutyronitrile (AIBN) as an initiator. Of the many reaction solvents tried, dimethylformamide (DMF) was found to be the solvent of choice especially for a large-scale synthesis. Alkaloid monomers employed were free dalkaloids, such as quinine, quinidine, cinchonidine, and cinchonine, and modified ones including 9-O-ethoxycarbonylquinine and quinine salts. The copolymers were thermally stable powders, soluble in DMF and DMSO, and insoluble in common organic solvents. They were found to be converted into water-soluble polymeric alkaloids by hydrolysis with alkaline hydrogen peroxide.
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  • 13
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 241-249 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A previously developed model which has been used to describe the kinetic behavior of free radical polymerization in the region of the gel effect is here subjected to a detailed quantitative examination. It is shown, using data for the polymerization of methyl methacrylate, that the quasi-steady-state assumption is valid during the gel effect, and that the model provides a good description of the chain lengths and concentrations of different species present in the reaction. The postulate that primary radical termination becomes important as the gel effect advances is tested and found to be true.
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  • 14
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 251-257 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Six recently proposed methods for analyzing copolymerization composition data have been compared to a nonlinear least-squares analysis to ascertain the precision of the six methods in determining reactivity ratios. Data used were simulated for five hypothetical monomer pairs with three different types of experiment design and contained error structures similar to those observed experimentally. The results of the comparisons suggest that retrospective analyses of existing copolymerization data should only be done with a nonlinear least-squares analysis. For new data, the design of experiments is of great importance, and when done properly allows the use of some of the linear least-squares methods of analysis.
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  • 15
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 275-281 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method of determining the degree of hydrolysis by potentiometric titration of polyacrylamide (PAA) with HCl and NaOH was developed. From the titration curves and the control of the degree of purity it is possible to calculate the level of hydrolysis and the quantity of pure acid contained in the PAA of a commercial product.
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  • 16
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 355-357 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 17
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 349-353 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 18
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 371-372 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 19
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 365-370 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 20
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 21
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 527-531 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Results are presented which extend earlier findings on the transformation of insoluble crosslinked polysiloxanes into soluble linear polymers by selective aminolysis at crosslink sites. The present study provides evidence of a substantial steric effect and catalysis by 2-pyridone. The results with 2-pyridone are attributed to tautomeric catalysis which, to our knowledge, had not been observed before in substitution reactions at silicon. Evidence is also presented that unhindered, difunctional primary amines effect aminolysis with both amine groups to produce insoluble crosslinked polymer, presumably with silylamine functionality at crosslink sites.
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  • 22
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 949-958 
    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.
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  • 23
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 959-965 
    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.
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  • 24
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 967-985 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The transport of oxygen by diffusion from the environment into a gas stream was investigated as a model for the analogous process in a diffusion flame. The amount transported at steady-state conditions depended on the flow rate, diameter, and spatial orientation of the gas stream. A change of the same extrinsic parameters in a diffusion flame caused changes of burner surface temperature, maximum flame temperature, and flame height. These responses were correlated and yielded an overall activation energy of the rate-controlling reaction step in the combustion process equal to 49 kcal/mole. This value was the same for several types of diffusion flames examined and appeared to be associated with the CO/CO2 conversion process at the high-temperature flame boundary. Flame quenching was demonstrated to occur at a minimum fuel flow rate and minimum environmental oxygen concentration which were characteristic for a given fuel. Quenching conditions were related to the diffusion rate of oxygen into the product effluent stream. Quenching of a polymer flame by depletion of environmental oxygen was governed by the same processes. The effect of extrinsic parameters on polymer flames is discussed in Part II.
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  • 25
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1021-1034 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On irradiation with ultraviolet light, dialkyl-4-hydroxyphenylsulfonium salts undergo reversible photodissociation and in the process generate ylids and Brønsted acids. When the anions are nonnucleophilic in character, as, for example, BF4-, AsF6-, PF6-, and SbF6-, the strong acid which is produced is capable of initiating cationic polymerization. The polymerization of several monomers was carried out to demonstrate the general applicability of these new photoinitiators.
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  • 26
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1035-1046 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Diethynylphenyl ether (DEPE) was synthesized and its thermal polymerization studied by NMR, IR, and DSC techniques. DEPE is a crystalline solid that melts at 72-73°C and undergoes polymerization beginning at about 150°C. The heat of polymerization measured by DSC was 53 ± 2 kcal/mole. Thermomechanical analysis (TMA) of the fully cured resin showed softening behavior at temperatures in excess of 400°C. Weight loss up to 720°C was only 21%. A mechanism of polymerization based on the analysis of IR and NMR data for party polymerized material below 300°C is proposed.
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  • 27
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of N-methyl-substituted aromatic polyamides derived from the secondary aromatic diamines 4,4′-bis(methylamino)diphenylmethane, 3,3′-bis(methylamino)diphenylmethane, 4,4′-bis(methylamino)benzophenone or 3,3′-bis(methylamino)benzophenone and isophthaloyl dichloride, and terephthaloyl dichloride or 3,3′-diphenylmethane dicarboxylic acid dichloride was prepared by high-temperature solution polymerization in s-tetrachloroethane. Compared with analogous unsubstituted and partly N-methylated aromatic polyamides, the full N-methylated polyamides exhibited significantly lower glass transition temperatures (Tg), reduced crystallinity, improved thermal stability, and good solubility in chlorinated solvents.
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  • 28
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1071-1078 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A wide compositional range of copolymers of 1-cyclobutene carbonitrile (CBCN) and 1-bicyclobutance carbonitrile (BBCN) with common vinyl monomers was prepared in order to study systematically the effect of cyclobutane carbonitrile ring incorporation on the glass transition temperature (Tg). In general, the Tg's of the copolymers are increased in proportion to the weight percent of the small-ring monomer incorporated, but the 1,2-mode of incorporation raises Tg more than the 1,3-mode. Attempts were made to correlate data with quantitative Tg-composition relationships (Fox-Johnston equations). Prediction for nitrile homopolymer Tg's are compared with literature values.
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  • 29
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1061-1070 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Proton relaxation measurements have been used to investigate the effects of crosslinking on the segmental motion in cis-1,4-polybutadiene samples. The temperature dependence of proton spin-lattice relaxation time T1 and spin-spin relaxation time T2 at 60 and 24.3 MHz are reported in cis-1,4-polybutadiene (PB) samples with different crosslink density including uncrosslinked PB and samples with 140, 40, and 14 repeat units between crosslinks. In addition, spin-lattice relaxation times in rotating coordinate frame, T1p, have also been determined. The relaxation data are interpreted in terms of the effects of crosslinks on segmental chain motions. Because of their sensitivity to low-frequency motion, T2 data are of major interest. At temperatures well above the T1 minimum the small T2 temperature dependence resembles solidlike behavior reflecting the nonzero averaging of dipolar interactions due to anisotropic motion of the chain segments between crosslinks. The magnitude of T2 at 60°C is found to be proportional to the average mass between crosslinks.
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  • 30
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1079-1087 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The molecular weight distribution of fractionated and unfractionated polystyrene samples has been determined by temperature drop turbidimetry, in which polymer is precipitated from dilute solutions in cyclohexanol by progressively cooling from 388 to 310 K. Estimates of the molecular weight averages and the polydispersities, obtained by calibration of the temperature of initial onset of precipitation, Ti, and the weight-average molecular weight were low, but could be substantially improved by correcting for concentration changes during precipitation. An empirical procedure correlating the breadth of turbidity-temperature curves to the logarithm of the polydispersity, as measured by gel permeation chromatography, appeared to be a simpler method of characterizing the polymer samples and as accurate as the computational methods above.
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  • 31
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1089-1097 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general solution is presented for the kinetics of an A-A plus B-C step polymerization. B and C are the same type of functional group but with different reactivities (k1 and k2, respectively) toward A groups. The decay of the concentrations of B, C, and A groups and the increase in the degree of polymerization with time are described for various values of the ratio k2/k1.
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  • 32
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1099-1104 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyterephthalamides of high molecular weight (ηinh up to 1.9) were obtained by the direct polycondensation reaction of terephthalic acid and aromatic diamines in the presence of poly(ethylene oxide) (PEO) with triphenyl phosphite in a N-methylpyrrolidone (NMP)-pyridine solution that contained lithium chloride. The molecular weights of the polymers produced varied with the amount and molecular weight of PEO, which showed maximum values when PEO with a molecular weight of 2.0 × 104-5.0 × 105 was used in a concentration of about 0.5 wt % in the solvent. The polycondensation reaction was significantly affected by the level of pyridine in a mixed solvent of NMP and pyridine and by the concentration of the lithium chloride added.
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  • 33
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1297-1323 
    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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  • 34
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1325-1337 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radiation-induced terpolymerizations of methyl α,β,β-trifluoroacrylate (MTFA) with tetrafluoroethylene (TFE) and α-olefins, such as ethylene, propylene, and isobutylene, were carried out in bulk at 25°C for the purpose of controlling the content of ester group in the MTFA-α-olefin alternating copolymers. These monomers polymerized to form alternating terpolymers which contained 50 mole % α-olefin in a wide range of monomer composition. The content of MTFA, namely, the ester group in polymer, can be varied without destruction of the alternating structures between fluoroolefins (MTFA, TFE) and α-olefin by changing the MTFA/TFE ratio in the monomer mixture. The relative reactivities of MTFA and TFE in the terpolymerization were discussed according to kinetic treatments by free propagating and complex mechanisms. The relation between the MTFA/TFE ratio in the monomer mixture and that in terpolymer was explained favourbly by the complex mechanism. It was also concluded that the relative reactivity of MTFA is larger than that of TFE in the terpolymerizations.
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  • 35
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    Notes: Sequential gas-liquid chromotographic analysis of the reaction mixture throughout a copolymerization reaction in conjuction with the improved curve-fitting I (integrated form) method, which accounts for measurements errors in both variables, allows accurate estimation of the monomer reactivity ratios. In this article an alternative method is presented for estimating r values in copolymerization with linear regression only, which is especially suited to cases in which one or two of the r values is close to 1. In these cases the improved curve-fitting I method tends to converge slowly because of the numerical instability of the integrated copolymerization equation. The use of the new method is illustrated for the estimation of the r values for ethylene and vinyl acatate in benzene at 35 kg/cm2 and 62°C. The linear regression method was also tried on other copolymerizations and the results are compared with those obtained from the improved curve-fitting I method. The limits of the applicability of the linear regression method were determined by simulated sequential sampling experiments. It appears that the new method is applicable when the product of the r values is between 0.001 and 2, provided both monomer conversions are large enough compared with the measurements error.
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  • 36
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1339-1346 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Investigations were performed on acetone and benzene-sensitized degradation of triethylene glycol (TEG), polyethylene glycol 400 (PEG 400), and polyethylene glycol 4000 (PEG 4000) in aqueous solutions exposed to irradiation at λ = 254 nm and λ ∼ 313 nm. The systems investigated were exposed at 20°C (±1°C) in both deaerated and undeaerated solutions. The course of the photosensitized degradation was examined viscosimetrically. The determined quantum yield (φ) of chain scission decreases distinctly as the molecular weight of the polymer rises, irrespective of the wavelength of the light absorbed and deaeration of system exposed.
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  • 37
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1359-1366 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Small-angle x-ray scattering methods were applied to calculate macromolecular parameters like specific inner surface (O/V), length of coherence (lc), and the percentage of air present in agave hybrid, treating it as a densely packed colloidal system belonging to a general micelle system. The parameters were equal to O/V = 8.50 × 10-6 Å-1, lc = 150 Å, and the percentage of air = 0.03. The Kratky camera with latest design was used for the experimental measurement. Because the sample agave ybrid is a natural fiber and a highly oriented system that is celluosic in character, the theories of Kratky and Porod have been used to evaluate these parameters.
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  • 38
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1367-1373 
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    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.
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  • 39
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1387-1397 
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    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.
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  • 40
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  • 41
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1433-1446 
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    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.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1459-1469 
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    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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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1447-1458 
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    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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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1483-1488 
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    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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  • 45
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1471-1481 
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    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.
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  • 46
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1499-1509 
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    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.
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  • 47
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    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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  • 48
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1511-1521 
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    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.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1633-1634 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1635-1637 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1639-1642 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1643-1646 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1647-1650 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1651-1664 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The absolute and relative binding energies for the C1s, O1s, and F1s core levels have been determined using x-ray photoelectron spectroscopy (ESCA) for a series of aliphatic, aromatic, and fluorine-containing polycarbonates. Comparisons of these experimentally determined, core-level binding energies with theoretical calculations using the ground-state potential model in the CNDO/2 SCF MO formalism as well as model compounds have been made on the C1s and O1s core levels. The degree of polymerization for low-molecular-weight fluorine-containing polycarbonates, as determined from ESCA measurements, is compared to measurements by vapor-phase osmometry and 19F-NMR.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1807-1813 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Alkaline hydrolyses of p-nitrophenyl-3-indoleacetate (p-NPIA) and N-(indole-3-acryloyl)imidazole (IAI) were studied in the presence of poly(4-vinyl-N-propylpyridinium bromide) (C3PVP), poly(4-vinyl-N-benzylpyridinium chloride) (BzPVP), and copolymers of 4-vinyl-N-benzylpyridinium chloride and 4-vinyl-N-cetylpyridinium bromide (C16BzPVP). The hydrolyses were enhanced by the addition of these cationic polyelectrolytes. The magnitudes of the enhancement were in the order C16BzPVP 〉 BzPVP 〉 C3PVP, which is explainable in terms of the hydrophobicity of the polymers. The result and activation parameters obtained indicated that the substrates bound to polymers were more reactive than free substrates. The association constants obtained from the kinetic measurements (K) increased in the order BzPVP 〈 C3PVP 〈 C16BzPVP, which may suggest an important contribution of charge transfer interaction, in addition to electrostatic and hydrophobic interactions, between the polymers and the substrates. The association constants between the polymers and IAI were also obtained independently from the spectrophotometric measurements (K*) with the charge transfer absorption bands. The lack of a satisfactory agreement between K and K* is discussed.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1815-1820 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The complex formation of flavin mononucleotide (FMN) with tryptamine, indoleacetate, and trytophan was investigated in the presence of polyelectrolytes; that is, sodium polyethylene sulfonate (NaPES), sodium polystyrene sulfonate (NaPSS), and a copolymer of diethyldiallylammonium chloride and sulfur dioxide (DECS). The complexation of FMN and tryptamine was strongly retarded by the macrocations and macroanions, whereas that of FMN and indoleacetate was enhanced by the macrocations. Furthermore, the equilibrium constants of FMN-tryptophan complex were insensitive to the addition of polyelectrolytes. These results suggest that the complexation of FMN was strongly influenced by the electrostatic interactions between the reactant ions and macroions, in addition to those between the reactant ions, in conformity with the secondary salt effect.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1821-1834 
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    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 the acid chloride of bis-m-carboxyphenyl acetylene (XII), isophthaloyl chloride (XX), diphenyl ether (XVIII), and 4,4′-diphenoxydiphenyl sulfone (XIX) in a Friedel-Crafts-type polymerization. These polymers were cured by Diels-Alder cycloaddition with 1,4-diphenyl-1,3-butadiene. The cured polymers showed an increase in Tg and in thermal and heat stabilities. The polymers form colorless, transparent, brittle films and can be cast into a glass fiber laminate. Both meta-and para-substituted acid chlorides of biscarboxyphenyl-1,3-butadiene yielded insoluble polymers under the same conditions but form processable polymers where combined with acetylene units in the polymer chain. Polymers that contained both acetylene and butadiene units were prepared but could not be cured by an intramolecular Diels-Alder cycloaddition reaction.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1835-1840 
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    Topics: Chemistry and Pharmacology
    Notes: New processable polyaromatic amides were prepared from the acid chloride of bis-m-carboxyphenyl acetylene (V), the acid chloride of 1,4-bis-m-carboxyphenyl-1,3-butadiene (VI), and several aromatic diamines. The polyamides that contained acetylene units were cured by Diels-Alder cycloaddition reaction with 1,4-diphenyl-1,3-butadiene, whereas the polyamides with 1,3-butadiene units were cured with N-phenyl maleimide. Cured polyamides showed an increase in tg, thermal, and heat stabilities. The polyamides can be cast into films and produce good glass-fiber laminates.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1841-1846 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(α-amino acid)s of high molecular weight were obtained by the direct polycondensation reaction of α-amino acids in the presence of polyvinylpyrrolidone (PVP) as a matrix of triphenyl phosphite and LiCl in N-methylpyrrolidone (NMP). Molecular weights of the polymer produced were improved by use of an increasing amount of matrix of higher molecular weight. Most favorable results were obtained by the reaction at 80°C for 16 hr at a monomer concentration of 0.33 mole/liter in a NMP solution that contained about 3 wt % LiCl in the presence of an equivalent unit mole of PVP with the molecular weight of 3.6 x 105. The polymer from β-alanine with high molecular weight, which is difficult to obtain by the NCA method, was easily prepared by this process.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1847-1856 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copolymers of L-lysine and L-lysine derivatives which contained nucleic acid bases substituted on the Nε position were synthesized by grafting nucleic acid derivatives onto poly-L-lysine. The conformation and interaction of these copolymers in solution were studied by using spectroscopic measurements. They existed in helical conformation at neutral pH values, and the polymer complex formation among them was examined by ultraviolet (UV) measurements in organic solvents. A decrease in the nucleic acid base content of the copolymers resulted in a decrease in helical structures and also in interactions with the polymer-containing complementary bases.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1889-1903 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of new fluorinated ketone-containing polymers, poly(p-vinyltrifluoroacetophenone) (PVTFA), poly(p-vinyldifluoroacetophenone) (PVDFA), poly(p-vinylphenylheptafluoropropyl ketone) (PVHFK), and poly(o-and p-vinylbenzyltrifluoromethyl ketone) (PVTFK), were prepared by the free radical polymerization of the corresponding monomers. The monomers, p-vinyltrifluoroacetophenone (VTFA), p-vinyldifluoroacetophenone (VDFA), p-vinylphenylheptafluoropropyl ketone (VHFK), and o-and p-vinylbenzyltrifluoromethyl ketone (VTFK), were prepared by the reaction of Grignard reagent with the corresponding perfluoroacid or its lithium salt. Polymerization was a competitive side reaction during monomer preparation. Reduced side reaction and higher yields of monomer (based on the Grignard reagent) were obtained from the lithium salt of the perfluoroacid, compared with the perfluoroacid itself. These new substituted polystyrenes which contain fluorinated ketone functionality were characterized by their ability to (1) react with active hydrogen compounds such as alcohols or water; (2) have high glass transition temperatures and decreased solubility in nonpolar solvents (e. g., benzene) compared with polystyrene; and (3) be converted into other functional groups such as alcohols or acids by treatment with the appropriate chemical reagents. Beads of a styrene (ST) terpolymer with 2% divinylbenzene (DVB), which contained the CF3COCH2 function, were prepared by suspension polymerization of ST, VTFK, and DVB. The terpolymer, which contains 15-17% mole (or 0.70-0.71 meg/g) of CF3COCH2 swollen with a solvent, were shown to chemisorb alcohols.
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  • 62
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1911-1916 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In an attempt to determine the role of a variety of amines in ceric-ion-initiated grafting, poly-(methyl methacrylate) was graft copolymerized onto Himachali wool in the presence of a variety of amines that included ammonia, diethylamine (DEA), dipropylamine (DPA), triethylamine (TEA), triethanol amine, and pyridine. All amines (with the exception of DEA) reduced the percent grafting. The reactivity of various amines toward graft copolymerization followed the order: DEA 〉 DPA 〉 NH3 〉 TEA 〉 triethanol amine 〉 Py. An explanation based on the basicity, nucleophilicity, and steric requirement of amines is given to explain the observed reactivity order shown by the various amines toward graft copolymerization.
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  • 63
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1917-1922 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermal decomposition of α,α′-azobisisobutyronitrile (AIBN) and dimethyl α,α′-azobisisobutyrate (MAIB) in the presence of a large amount of tin tetrachloride was investigated to determine the effect of complex formation on the decomposition rates and yields of the recombination products. The addition of tin tetrachloride significantly increased the decomposition rates; the observed first-order rate constant increased by factors of 4.5 and 17 at molar ratios of [SnCl4]/[AIBN] = 21.65 and [SnCl4]/[MAIB] = 19.53, respectively. It was found that the decomposition of these azo compounds was also accelerated by the addition of a comparable amount of donor solvent such as ethyl acetate or propionitrile to tin tetrachloride and that the enhancement in rate was accounted for by a larger frequency factor in the Arrhenius equation. Furthermore, the addition of tin tetrachloride seemed to suppress the formation of recombination products, tetramethyl succinonitrile and dimethyl tetramethylsuccinate, of the radicals produced by decomposition.
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  • 64
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1923-1931 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Direct pyrolysis in the mass spectrometer (MS) yielded unequivocal evidence regarding the mechanism of thermal decomposition of N-monosubstituted and N-disubstituted polyurethanes. It was ascertained that direct pyrolysis in the MS detects the primary thermal fragments that originate from polyurethane pyrolysis. This is particularly useful when, as in the thermal decomposition illustrated in eq. (1), it is necessary to distinguish between primary and secondary thermal fragments in order to assess the thermal degradation mechanism. Our results indicate that N-monosubstituted polyurethane V undergoes a quantitative depolycondensation process. Instead, the thermal decomposition of the N-disubstituted polyurethane VI which occurs selectively in eq. (1) is demonstrated by the detection of thermal fragments that contain secondary amine and olefinic end groups. Finally, polyurethane VI shows a higher thermal stability with respect to polymer V because of the absence of the depolycondensation process, which accounts for the thermal degradation of the N-monosubstituted polyurethane V.
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  • 65
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1933-1943 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radical polymerization of N-vinylpyrrolidone along poly(methacrylic acid) templates of high syndiotatic content was followed dilatometrically in dimethylformamide, which was used as solvent. The effects of template concentration, template molar mass, and temperature on polymerization rate and average molar mass of the formed polyvinylpyrrolidone (PVP) were examined. Template concentrations were varied around the critical concentration for homogeneous segmental distribution, C*. Below this concentration, template coils can act as separate microreactors wherein growing PVP radicals exhibit maximum rate enhancement, i. e., relative rate νR = νR,max. In the free solution, blank polymerization occurs, i. e., νR = 1. Consequently, νR can be approximated by the equation νR = φνR,max + (1 - φ), where φ represents the volume fraction occupied by template coils. The slight increase in UR and PVP molar mass with the template chain length is supposed to be caused by the influence of translational diffusion on the termination step. Over the investigated temperature range of 50-70°C, the activation energy and entropy were almost identical for blank and template polymerization. An expected decrease of ΔE≠ and ΔS≠ in template systems is supposed to be compensated by the effects of desolvation of the template macromolecules during the propagation step.
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  • 66
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1945-1956 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polystyryllithium was prepared by anionic polymerization. This “living polymer” and the polystyrylmagnesium bromide derived from it were treated with carbon dioxide (solid or gas). The highest yields of carboxylic acid were obtained when solid carbon dioxide was used with polystyryllithium or by treatment of polystyrylmagnesium bromide with gaseous carbon dioxide. The products from the reaction of polystyryllithium with oxygen were polymeric ketone X, the alcohols IXa and IXb, and coupling products (e. g., XI). The various functionalized and unfunctionalized polystyrene products were isolated by chromatography on silica gel and were characterized by gel permeation chromatography (GPC), thin layer chromatography (TLC), and high-performance liquid chromatography (HPLC) in combination with chemical transformations.
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  • 67
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1957-1966 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A technique has been developed for initiating a graft copolymerization electrochemically. A copoly(styrene/vinylbenzophenone) linear copolymer was prepared to serve as the electroactive starting material. The benzophenone sites on this molecule are readily activated at the cathode. Macroradical ions result from the direct transfer of electrons to benzophenone groups of the electroactive backbone polymer. In solution in N,N-dimethylformamide with tetraethylammonium perchlorate (TEAP) as supporting electrolyte the passage of current produced a dark blue solution similar to that observed with radical anions obtained with benzophenone directly. When monomer such as acrylonitrile or methyl methacrylate was added, a graft copolymer was formed. Electrolysis of solutions of the backbone polymer in tetrahydrofurn (THF), with sodium tetraphenylboride as supporting electrolyte, produced relatively stable, persistent macroradical anions and, under appropriate conditions, the reddish-violet macrodianions. Both types initiated graft copolymerization of acrylonitrile and methyl methacrylate. Graft copolymers were characterized by gel permeation chromatography (GPC), infrared (IR), and solvent extraction. High grafting efficiency (i. e., free from homopolymer) can be obtained under appropriate conditions. Suitable mechanisms are proposed, compared, and discussed.
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  • 68
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1967-1977 
    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 block co-and terpolymers is described. Fully acetylated amylose triacetate was hydrolyzed by hydronium ions to give a hydroxy-terminated amylose triacetate oligomer (HATA), which was reacted with diisocyanates to produce block copolymers. Prepolymers of HATA and MDI or TDI were reacted with both hydroxy-terminated polybutadiene and polypropylene glycol to form block terpolymers. Block co- and terpolymer formation was demonstrated by intrinsic viscosity increases, gel permeation chromatographic results, and NMR and IR spectroscopy. The products were easily deacetylated by NaOMe in methanol to yield amylose block co- and terpolymers. These polymers were readily degraded by α-amylase. The enzymatic hydrolysis was monitored by intrinsic viscosity measurements. The rate of biodegradation was influenced by the DS of the amylose block and the composition of the block terpolymers.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1979-1993 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: As the first phase in the study of the emulsion polymerization of acenaphthylene (AcN), the oligomerization kinetics of the in-aqueous-phase soluble portion of the AcN monomer was investigated. The reactions were carried out in the absence and presence of anionic emulsifiers. The monomer disappearance rate was followed by ultraviolet (UV) spectroscopy and spectra were established for these species. It was found that aqueous phase AcN oligomerized with K2S2O8 initiator at 50°C to yield SO-4K+ -ended oligo -AcN species which showed a UV hypsochromic shift in polar solvents. The oligomerization had a second-order dependence on monomer concentration. The presence of sodium oleate (SO) and sodium dodecyl sulfate (SDS) emulsifiers at below and above their critical micelle concentrations decreased the rate constant of the aqueous phase oligomerization. These observations led to the suggestion of a mixed micellization concept in the particle nucleation mechanism.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1995-2000 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Improved methods for the synthesis of 4-halogeno 1-vinylnaphthalenes are proposed. Reactivity ratios are determined for the following systems: 4-fluoro-1-vinyl naphthalene-styrene, 4-chloro-1-vinyl naphthalene-styrene, and 4-bromo-1-vinyl naphthalene-styrene. The determinations are performed at various specific temperatures and the relative activation parameters are obtained. It appears that the reactivity of 1-vinyl naphthalene is drastically decreased when substituted by a halogen. In the case of 1-vinyl naphthalene the selection is enthalpically controlled.
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  • 71
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2001-2010 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetics of the polymerization of acrylonitrile has been investigated in aqueous sulfuric acid in a temperature range of 25-45°C. The rate of polymerization (Rp) and the rate of managanic ion disappearance, etc., have been measured. The effect of the various additives, such as water-miscible organic solvents, neutral electrolytes, complexing agents, and surfactants, on the rate has been thoroughly studied. A mechanism that involves the initial complex formation between the thiol form of the thioamide and Mn3+, whose decomposition yields the initiating free radical with the polymer chain terminated by mutual combination of growing radicals, has been suggested.
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  • 72
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of block copolymers in three-step reactions from linear polycondensates (e.g., nylon 6. nylon 6,6, nylon 6,10 and polyurethane) and olefinic monomers (e.g., styrene, acrylic acid and acrylonitrile, methyl methacrylate, vinyl acetate, vinyl chloride, and isoprene) is reported. Macromolecular radicals are formed by the thermal decomposition of partly nitrosated peptide group containing polycondensates at elevated temperatures (60-200°C). These polyradicals initiate the copolymerization of the olefinic monomers. The conversion and reaction rates were generally high (up to 100% within a few hours). Most of the block copolymers prepared were soluble in organic solvents. Some, however, were insoluble or rubberlike. The reaction mechanism involved are analyzed. Applications are discussed.
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  • 73
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2033-2043 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The action of hydrazine on desulfurized tetrasulfide polymer obtained from bis-2-chloroethyl formal leads to S—S bond splitting and depolymerization. Our studies show that successful depolymerization can be initiated only in a strong alkali medium at 95-98°C. During this process cleavage of the disulfide bonds and the formation of polymers of lower molecular weight with —SH end groups takes place. From the results of the experiments performed it can be seen that the degree of depolymerization increases with an increase in the amount of hydrazine, in the mole ratio of sodium hydroxide, and in the time of reaction. When 0.7-1.0 mole of hydrazine per segment of polymer and 4 mole of sodium hydroxide per mole of hydrazine are used, a polymer of low average molecular weight in the form of water-soluble sodium salt (fraction I) and a polymer in dispersion form (fraction II) are obtained. Similar results could be attained if the amount ot hydrazine were decreased and the mole ratio of sodium hydroxide were simultaneously increased to more than 4 mole per segment of hydrazine used. In a constant amount of sodium hydroxide with a smaller quantity of hydrazine or a shorter reaction time the amount of water-soluble polymer (as a sodium salt) decreases and the amount of polymer in dispersion form increases. If a portion of the polymer in dispersion is coagulated with a portion of the polymer in the mother liquid, the yield of the depolymerized product is higher, but the average molecular weight is also higher than those of fraction I. The influence of the average contents of sulfur on the efficiency of the depolymerization is tested in polymers that contain 2.5 (i.e., 3) atoms of sulfur per segment of polymer. The result is that the depolymerization of the polysulfide polymer could be carried out without previous desulfurization, but the molecular weights of the products obtained with an equivalent quantity of hydrazine are much higher than those obtained by depolymerization of the disulfide polymer.
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  • 74
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2045-2050 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetics for the polymerization of ethylene and the copolymerization of ethylene and propylene were studied by using highly effective heterogeneous metal organic catalysts produced by coating different organic and inorganic supports with the components of Ziegler systems. The activity of a supported Ziegler catalyst is characterized by the physical parameters of the support structure and its chemical nature. The active role of magnesium-containing supports was established for the formation and functioning of the propagating species on their surfaces. This role is expressed not only by an increase in the portion of transition metal included in the propagating species, compared with typical Ziegler catalysts, but also by an increase in the reactivity of the propagating species, change in the nature of the elementary processes for polymerization and copolymerization, including control of copolymerization constants, and modification of the molecular structure of the polymers and copolymers. It was shown that by choice of support it is possible to control the activity of the same catalytic system and characteristics of the structure and properties of the polymers it produces under identical polymerization conditions.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2121-2128 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Alloxan or ninhydrin radical anions which are obtained from alloxantin or hydrindantin, respectively, by treatment with triethylamine could be trapped in stable condition by polymer cations that contains 1-benzyl-3-carbamoyl pyridinium or 1-benzylpyridinium salts structure.
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  • 76
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2103-2119 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The air oxidation of poly-p-xylylene films was studied at temperatures between 125 and 200°C. The oxidation kinetics were obtained from neutron activation (NA) oxygen analyses and infrared (IR) Spectroscopy. A correlation between the NA oxygen analyses and mechanical properties indicated that the amount of oxygen incorporated into these polymers before a significant degradation mechanical properties is about 1000 ppm for poly(dichloro-p-xylylene) and 5000 ppm for poly(monochloro-p-xylylene) or poly-p-xylylene. The activation energy for the oxidation of these polymers was about 30 kcal/mole. Long-term-use (100,000 hr) temperatures were also estimated for each of the poly-p-xylylenes studied. The 100,000-hr maximum continuous-use temperature is 112°C for poly(dichloro-p-xylylene), 72°C for poly(monochloro-p-xylylene), and 57°C for poly-p-xylylene.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2143-2153 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radical-induced grafting of styrene onto polyisoprene (PIP) in benzene solution at, 60°C was studied in rubber concentration (up to 0.5 monomer mole liter-1) in which the polymerization of styrene shows ideal kinetics with no retardation by PIP. The proportion of polystyrene incorporated as graft is independent of the initiator (benzoyl peroxide) concentration and was found to be consistent with the kinetic expression derived by Cameron et al. The graft fraction of polystyrene which is higher than in the corresponding styrene-polybutadiene system reflects the higher reactivity of PIP toward radicals. Azobisisobutyronitrile produces no graft copolymer in this system.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2163-2174 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of polyamides which contained thianthrene, phenoxatiin, and dibenzo-p-dioxin units was synthesized from tricyclic fused-ring diamines and aromatic diacid chlorides by solution polycondensations at a low temperature. The amorphous polyisophthalamides were highly soluble in polar organic solvents, whereas some of the polyterephthalamides with a fair degree of crystallinity were insoluble. The solubility of the series of polyamides increased in the order of the dibenzo-p-dioxin-containing polymers 〈 phenoxatiin-containing polymers 〈 thianthrene-containing polymers. The thermal stability increased in the reverse order and the dibenzo-p-dioxinpolyamides were more thermostable than the corresponding open-chain polymers with diphenyl ether linkages. The polyamides derived from 2,8-oriented tricyclic diamines showed somewhat lower glass transition temperatures than those from 2,7-oriented diamines.
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  • 79
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyphosphate and polyphosphonate esters of molecular weights 〉 10,000 were synthesized by base-promoted, liquid-vapor and liquid-liquid interfacial polycondensations of hydroquinone (HQ) with 4-methylthiophenyl phosphorodichloridate (MTPP) and phenylphosphonic dichloride (PPD). The barium hydroxide-initiated liquid-vapor polycondensation of PPD and HQ in the temperature range of 15-95°C shows that [η] increases with reaction temperature and unfractionated yields exhibit a maximum at about 45°C. The analogous liquid-vapor polycondensation of MTPP and HQ between 25 and 854C also shows a maximum yield at 45°C, whereas [η] decreases with increase in reaction temperature. The results are contrasted with temperature dependencies of base-catalyzed, liquid-liquid polycondensation of HQ with MTPP and PPD. A different insight is obtained by analyzing the temperature effects on fractionated products. The relative importance of degradative saponification reactions are ranked as attack on chain ester linkages 〉 phosphorus chloride reactant 〉 end groups of growing chains.
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  • 80
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2189-2196 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polycondensation of bis-N-hydroxyimides, N,N′ dihydroxypyromellitic diimide, and N,N′ -dihydroxybenzophenonetetracarboxylic diimide with dicarboxylic acid chlorides was carried out in dimethylacetamide in the presence of triethylamine to produce novel polyimide-esters. The resulting polymers had inherent viscosities up to 0.27 dl/g. These polyimide-esters and model compounds exhibited high reactivity toward nucleophiles such as aniline and n-butylamine, which brought about rapid reductions in the viscosity of the polymers. These polymers were fairly resistant to organic solvents but soluble in m-cresol. Thermal stability oft he polyimide-esters was evaluated by thermogravimetry and their good heat-resistant properties were confirmed.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2209-2219 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vinyl copolymers with pendant porphyrin dimers were synthesized first by the dimerizations of chlorophyll-α and protoporphyrin IX via the ethylenebisamide linkage, then by copolymerization of the vinylbenzyl esters of the resulting dimers with N-vinylpyrrolidone or the esterification reaction of the dimers with chloromethylstyrene copolymers. Dimer-pendant copolymers with vinyl pyrrolidone catalyzed photoredox systems in aqueous solutions more efficiently than the corresponding monomer analogs, presumably because of the interactions exerted between the two combined porphyrin rings, which are manifested in the hypochromic effect in absorption spectra. The effect of the central Mg atom in the protoporphyrin IX ring was also considerable.
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  • 82
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2197-2207 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radical polymerization and copolymerization of some o-alkylphenyl methacrylates were carried out and the effect of the ortho-substituents on the ability to homopolymerize, on the monomer reactivities, and on the ceiling temperatures of the monomers was studied. The effect of the substituent on tacticities and thermal stabilities of the polymers formed was also discussed. The ability to honiopolymerize and the monomer reactivity were considerably decreased by the introduction of the o-substituent. 2,6-Di-tert-butylphenyl methacrylate formed no methanol-insoluble polymer at 60°C. On the basis of the tacticity determined it was noted that the o-substituted phenyl methacrylates preferred syndiotactic addition in the propagation reaction less than did phenyl methacrylate or methyl methacrylate. The polymers formed from the o-substituted monomers were thermally less stable than poly(phenyl methacrylate), and, consistent with this finding, ceiling temperatures of the o-substituted phenyl methacrylates seemed to be lower than that of phenyl methacrylate. The effects observed were characteristic of the o-substituents conformationally close to the carbon-carbon double bond of the monomer or the carbon carrying the unpaired electron of the polymer radical.
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  • 83
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2221-2238 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Studies have been made of the photochemistry of ethylene copolymers with carbon monoxide (CO), methyl vinyl ketone (MVK), and methyl isopropenyl ketone (MIPK) in solid films. Infrared (IR) evidence is presented to show that a variety of unexpected ketone structures is present in these polymers as a result of 1,5-hydrogen transfer or “back-biting” during the high-pressure polymerization reaction. These additional structures complicate the analysis of the quantum yield data. The overall quantum yield for carbonyl disappearance (φ-co) which increases from 0.074 to 0.24 to 0.26 in the series PE-1% CO, PE-2% MVK, and PE-20% MIPK reflects the increasing stability of the alkyl radicals produced from the type I process in the respective ketone structures. It is also shown that ketone groups located in the backbone of the polymer, as in the 1% CO copolymer, have lower quantum yields for photochemical reactions, particularly those that produce free radical intermediates. Studies of the gaseous products from extensive photodegradation under nitrogen show that in all three cases carbon monoxide is the major product (46-65% of the total). Acetaldehyde and methane, expected from the type I reaction, are major products only for the MVK and MIPK copolymers. Reaction schemes are presented to explain the major products observed.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2239-2246 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The copolymerization of acrylonitrile (r1) and p-acetoxystyrene (r2) in bulk yields reactivity ratios r1 = 0.08 and r2 = 0.42. Crosslinked resins are readily obtained by a new type of precipitation copolymerization of acrylonitrile, p-acetoxystyrene, and divinylbenzene. After deacetylation, the phenolic groups afford useful attachment sites for protected amino acids as a first stage in solid-phase peptide synthesis. Reactivity of typical 10% functionalized polyacrylonitrile-based resins is comparable to that of the more usual polystyrene-based equivalents, although swelling characteristics of the two types of resin are very different.
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  • 85
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2247-2255 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The graft copolymerization of methyl methacrylate (MMA) onto silk in aqueous media initiated by the potassium peroxydiphosphate-thiourea redox system was studied at 50°C. The rate of grafting was determined by changing [monomerl], [thiourea], [initiator], acidity of the medium, reaction medium, and temperature. A significant increase percent of grafting was noticed with increasing monomer concentration to 84.49 × 10-2 mole/liter and the further increase is associated with the decrease of graft yield. The graft yield increases with an increase of thiourea (Tu) concentration to 25 × 10-5 mole/liter; then it decreases. A measurable increase in graft yield was observed with an increase in acidity of the medium. Graft yield increases to a certain temperature, i.e., 50°C, and then it decreases. The graft yield increases with an increase of initiator concentration to 60 × 10-4 mole/liter; then it decreases. The graft yield is medium dependent. A suitable kinetic path has been proposed and the rate equation has been derived.
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  • 86
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2257-2265 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A detailed kinetic study of the γ-ray-induced surface grafting of methyl acrylate (MA) onto polyethylene (PE) has been investigated by using quartz helix microbalances. Under typical graft conditions, the grafting rate increases, levels off, and then accelerates with irradiation time; i.e., the typical growth process of the surface grafting consists of an initial stage having an increasing rate of grafting, an intermediate stage having a constant rate, and an advanced stage having an accelerated rate. A homopolymer layer (consisting only of an MA component) begins to be formed on the inner graft copolymer layer (consisting both of MA and PE components) at the transition zone in grafting rate after a duration of a constant rate of grafting. Therefore, the increasing rate in increasing rate in the intial stage of grafting reflects the graft copolymerization in the graft copolymer layer (inside the PE sheet), and the increasing rate in the advanced stage reflects the growth of the homopolymer layer. Under grafting reflects the graft tage reflects the growth of the homopolymer layer. Under grafting conditions by which the homolymer layer is not formed throughout the whole grafting process, the surface grafting remains remains in the initial stage. On the order hand, under grafting conditions by which the homopolymer layer begins to be formed from an early stage of grafting, the surface grafting proceeds rapidly from the initial stage to the advanced stage and thus skips the intermediate stage.
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  • 87
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2281-2291 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Macosko-Miller approach is used to obtain an expression for the polydispersity index for AA, BB, CC linear step polymerization system in which B and C are the same type of functional group. The dependence of the polydispersity index, as a function of the extent of reaction, on the monomer masses and on the relative reactivities of B and C groups toward A, is examined in detail.
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  • 88
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2293-2306 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of cyclopentadiene-blocked acrolein with α,β-unsaturated ketones, esters, and nitriles in the presence of a thiazoliurn salt under basic conditions led to a simple method for the preparation of acetonylmethyl Vinyl ketone, 2-carboxymethylethyl vinyl ketone, and 2-cyanoethyl vinyl ketone. In addition, the cyclopentadiene-blocked acetonylmethyl vinyl Ketone was converted to heterocyclic furan and pyrrole monomers.
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  • 89
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2267-2280 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Graft polymerization was carried out on carbon fibers subjected to various types of oxidation treatment and on acrylate (methyl, ethyl, and n-butyl) with benzene solvent and mainly benzoyl peroxide as initiator according to the nitrogen-displacement sealed-tube polymerization method. In comparison with carbon fibers subjected to air oxidation treatment, carbon fibers subjected to nitric acid oxidation treatment showed easier graft polymerization, and grafting became easier with increasing degree of nitric acid oxidation. The following relationship is established between the graft reaction ratio (a) and the polymerization time (t): da/dt = K(100-a). For graft polymerization with lauroyl peroxide (LPO), benzoyl peroxide (BPO), and α,α′-azobisisobutyronitrile (AIBN) as initiator, LPO showed the largest transfer reaction constant, followed by BPO; AIBN showed the smallest value. Grafting showed a tendency to become easier for monomers with a larger displacement radical group. For the graft polymerization reported in this article, it was believed that the affinity between carbon fibers subjected to oxidation treatment and to monomer influenced the result. For graft polymerization using acrylic acid as the comonomer, percent grafting increased notably. It is believed that, in this, in this case, apparent grafting by dipole-dipole interaction of the —COOH group of the carbon fiber subjected to oxidation treatment and the —COOH group of the polymer occurs according to the theory of Riess et al. Tensile strength and breaking elongation of graft carbon fibers showed a tendency to increase with an increase in percent grafting, whereas Young's modulus showed a tendency to decrease. The contact angle with water showed a tendency to increase with increasing percent, whereas the contact angle with ethylene glycol and phenylglycidilethyl showed a tendency to decreasing percent grafting.
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  • 90
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2347-2355 
    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 the addition reaction between poly(4-vinylpyridinium chloride) and electrophilic vinyl compounds, such as acrylic acid, acrylamide, methylacrylate, and acrylonitrile. leads to ammonium quaternary polymers with a transformation degree that depends oil the reactivity of vinyl compounds. The structure of addition compounds was established by using 1H-NMR IR, and UV spectral methods. NMR-determined values of transformation degree indicate that the reactivity of vinyl compounds decreases as follows: \documentclass{article}\pagestyle{empty}\begin{document}${\rm CH}_{\rm 2} \hbox{=\hskip-1.5pt=} {\rm CH} \hbox{---} {\rm COOH} 〉 {\rm CH}_{\rm 2} \hbox{=\hskip-1.5pt=} {\rm CH} \hbox{---} {\rm CONH}_{\rm 2} 〉 {\rm CH}_{\rm 2} \hbox{=\hskip-1.5pt=} {\rm CH} \hbox{---} {\rm COOCH}_{\rm 3} 〉 {\rm CH}_{\rm 2} \hbox{=\hskip-1.5pt=} {\rm CH} \hbox{---} {\rm CN}$\end{document}
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  • 91
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2357-2369 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Homogeneous trimethylsilylation of silicic acid in nonaqueous media was studied. The silylation process consisted of three steps: acidification of sodium silicate, solvent extraction. and trimethylation of silicic acid. Sodium silicate was first acidified with dilute sulfuric acid to form silicic acid: extraction followed with hydrophilic organic solvents. The Silicic acid obtained was finally allowed to react with trimethylchlorosilane to give trimethylsilylates with molecular weights of 1000-12,000. Optimum conditions for each step have been intensively sought to achieve trimethylsilylates in high yield. The trimethylsilylates exhibited excellent thermal stability and surface properties, such as water repellency and antifoaming properties, comparable to those of conventional polydimethylsiloxanes.
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  • 92
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2371-2390 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vinylpyridine-N-oxide units were introduced in polymeric chains in order to study their photocrosslinking. Copolymers of styrene and 4-vinylpyridine-N-oxide were especially synthesized and studied. The methods used for characterization of photocrosslinked films were a “photoresist test” or the measurement of the insolubility and of the swelling ratio. The Cleavage of the N-oxide bond was responsible for the photocrosslinking. The competitive formation of carbonyl compounds took place and decreased the rate of photocrosslinking. This last reaction is favored by triplet-state quenchers. The photosensitivity of the copolymers was determined as a function of the wavelength of the radiation used. When the photocrosslinking proceeded, a film of the copolymeric material became transparent in the 280-320-nm range. Thick films could therefore be completely photocrosslinked when irradiated in this range of wavelength.
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  • 93
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2391-2410 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Methyl-5-vinylpyridine-N-oxide, 4-vinylquinoline-N-oxide. 9-vinylacridine-N-oxide, p-N,N-dimethylaminostyrene-N-oxide units were introduced in polymeric chains as homopolymers or/and as styrene copolymers to study their photocrosslinking. The method used for characterization of photocrosslinked films was a “photoresist test” described in Part I of this series. The photosensitivity of the different chromophores bound to the different polymer has also been studied by UV, IR, and fluorescence spectrophotometries. The use of aromatic amine N-oxide groups in polymers seems to be a general means to produce their photocrosslinking by radical reactions. Among the different polymeric materials prepared, 4-vinylpyridine-N-oxide and 4-vinylquinoline-N-oxide are the most photosensitive.
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  • 94
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2423-2436 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A reinvestigation of the oligomeric and polymeric products obtained from furan and trichloroacetic acid was carried out to establish their structures. Comparison of spectral data with those of authentic materials indicated that the major oligomeric products are IV and V. The ratio of the products IV:V was 1:52. Comparison of the polymeric material with IV and V suggests that V is the primary component of the larger chains. In addition, microanalytical and molecular weight data were obtained. These findings are in disagreement with the structural designation of Wassermann et al., who proposed the presence of units that possessed aliphatic unsaturation (I), and of Kresta and Livingston, who put forth structure III for the same product. Mechanistic aspects are discussed. A limited study was carried out on insoluble polyfuran which was isolated from the reaction of furan with hydrochloric acid.
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  • 95
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2411-2422 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four typical bioactive esters of acrylic monomers, N-p-acryloxybenzoyloxysuccinimides, 3-ac-ryloxy-4-oxo-3,4-dihydro-1,2,3-benzotriazines, N-acryloxy-5-norbornene-2,3-dicarboximides, and I-p-acryloxybenzoyloxybenzotriazoles, were Synthesized and polymerized as reactive polymers. Twelve new monomers were prepared by coupling acrylic acid, methacrylic acid, p-acryloxybenzoic acid, or p-methacryloxybenzoic acid with four N-hydroxy compounds such as N-hydroxysuccinimide (HOSu), 3-hydroxy-4-oxo-3,4-dihydro-1,2,3-benzotriazine (HOObt), N-hydroxy-5-norbornene-2,3-dicarboximide (HONB), and I -hydroxybenzotriazole (HOBT) in the presence of dicyclohexylcarbodimide. All monomers polymerized readily in solution with azobisisobutyronitrile (AIBN) as free radical initiator. The resulting reactive polymers with reactive —OSu, —OObt, —ONB, or —OBT group on the side chain are equally reactive toward n-butylamine at room temperature in the formation of corresponding polyacrylamides. Reactive polymers were used to immobilizetrypsin. It has been found that poly(N-p-methacryloxybenzoyloxy-5-norbornene-2,3-dicarboximide)-trypsin matrix had high activity around three times that of the poly(N-methacryloxy-5-norbornene-dicarboximide)-trypsin matrix. It is proposed that this activity may be due to the presence of a long spacer arm with a hydrophobic and rigid benzene ring between the ligand and matrix. The reactive poly(N-p-methacryloxybenzoyloxysuccinimide-p-methacryloxybenzoic acid) copolymer was used to immobilize the serum protein. This immobilized protein was a hopeful bioactive solid immunoadsorbent.
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  • 96
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2437-2449 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymorphic behavior and γ-ray-initiated postpolymerization of the even-numbered long-chain Methacrylates (C18-C12) have been investigated. Phase transition behaviors of octadecyl, hexadecyl, tetradecyl, and dodecyl methacrylates are respectively, which become simpler with shortening of the chain length. The methacrylate monomers with sufficiently long hydrocarbon chains, such as octadecyl and hexadecyl, can be polymerized rapidly in the α-form crystal (hexagonal packing) by a fully two-dimensional mechanism, whereas in the β-form crystal (triclinic packing), polymerization can hardly occur. In the case of dodecyl methacrylate, however, an accelerated polymerization in the β form occurs after an induction period of several hours and the resultant polymer is gel-like. This can be interpreted by the propagation reaction across the polymer chain already formed. It has been found that the solid-state post-polymerization of n-alkyl methacrylates is affected by the chain length through the packing mode of the monomer molecules and also by the aggregation state of side chains in the resultant comblike polymer.
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  • 97
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2461-2470 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general detailed model of polymer oxidative degradation in the presence of a stabilizer-oxygen acceptor was considered. The motion of the degradation zone boundary and the sample lifetime were obtained for various conditions of the process. In particular, it is shown that within the given concentration immobile oxygen acceptor has the best stabilizing properties. The theoretical results are compared with the experimental data obtained by using two independent methods: polymer sample cracking and a change in the ESR signal. Good agreement between theory and experiment was obtained.
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  • 98
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of epoxy groups at the surface layer of ethyl acrylate-glycidyl methacrylate copolymer (1) emulsion particles on its crosslinking reactivity has been investigated. For this purpose two series of I emulsions were prepared. In the Y series, of which emulsion particles have epoxy groups at the surface layer, the epoxy content in the polymerization recipe was varied. For preparing the X series, of which emulsion particles have few epoxy groups at the surface layer, the high epoxy content of a given emulsion was reduced by various degrees of cleavage reaction with HCl-CaCl2. In emulsion blend films with amine-group-containing copolymer (II) emulsion, where the crosslinking reaction was expected to proceed only at the interfacial layer of I and II emulsion particles, the Y series, compared to the X series at the equal overall epoxy content in particles, showed less swelling and higher gel fraction in dioxane, less swelling in water, and higher tensile strength and modulus. On the other hand, this difference was not observed in the next two crosslinked films in which crosslinking was expected to be homogeneous. First, blends of I and II, which were isolated from the corresponding emulsions discussed above, were cast from dioxane solutions. Second, I emulsions were cast with BF3 ether complex which was expected to penetrate into the particles. It is concluded that the response of I emulsion cleaving the epoxy groups at the surface layer of particles to subsequent interfacial crosslinking is obviously reduced. However, even such an emulsion can be crosslinked to an extent similar to that of an uncleaved emulsion with similar overall epoxy content, if the crosslinking reaction is conducted so as to give an homogeneous effect.
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  • 99
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2471-2479 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of redox -initiated polymerization of acrylic acid (AA) by the systerm Mn3+-isobutyric acid (IBA) in sulfuric acid was studied in the temperature range of 35-50°C. The overall rates of polymerization (Rp), disappearance of manganic ion (-Rm), and degree of polymerization (Xn), were measured with variation in [monomer], [Mn3+], [IBA], H+, μ, [Mn2+], and temperature. The polymerization is initiated by the organic free radical that develops from the Mn3+-isobutyric acid oxidation reaction. Two types of termination reactions, one by the metal ion (Mn3+) and the other by the MN3+-isobutyric acid complex are proposed to explain the kinetic results. The various rate parameters were evaluated an discussed.
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  • 100
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Phthalimidomethyl 1,3-butadiene was homopolymerized and copolymerized with butadiene by free radical initiators; r1 and r2 were close to 1. All the attempts to polymerize 2PMB anionically have been unsuccessful. Preliminary studies of various η3-allylic catalysts showed that η3-allyl M0(CO)3OOCCF3 initiates the polymerization of butadiene and is not sensitive to N-methyl phthalimide (NMP); neither does it initiate the copolymerization of butadiene and 2PMB. On the other hand, a catalyst that results from the reaction of allyl trifluoroacetate with nickel tetracarbonyl is efficient for the copolymerization of butadiene and 2PMB. η3-Allyl nickel trifluoroacetate was prepared in heptane or benzene and used in benzene or methylene chloride. In all cases it initiated the copolymerization of butadiene with 2PMB
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