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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2023-2031 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conductance of acetone and methyl ethyl ketone solutions of tetraphenylborate salts in the presence of homopolymers and styrene copolymers of vinylbenzo-15-crown-5 and vinylbenzo-18-crown-6 was studied, and the results compared with data obtained for crown ethers. Polycations are formed on binding cations to the poly(crown ethers), and the conductance behavior of the polyelectrolytes depends on the nature of the cation-crown complex and the spacing between crown moieties which in turn determines the charge density on the polymer chain. The compositions of the crown-cation complexes were determined for crown ethers. The complex formation constants of sodium and potassium cations to poly(vinylbenzo-18-crown-6) were found to change as more cations bind to the chain. This is not the case for the copolymers where the crown ligands are spaced farther apart. A mixture of poly(vinylbenzo-15-crown-5) and 10-3M potassium tetraphenylborate in methyl ethyl ketone or acetone has a minimum conductance at a crown to cation ratio of 3.0, but the conductance rapidly increases on addition of crown ether. This was used to qualitatively determine the binding efficiency of a series of crown ethers since the rate of increase in the conductance is a measure of the binding ability of the crown ether to the cation.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1189-1197 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Insoluble polysalt complexes are formed on mixing aqueous solutions of poly(vinylbenzo-18-crown-6) (P18C6) and sodium carboxymethylcellulose (CMC) in the presence of certain salts. Potassium salts are especially effective, converting the neutral P18C6 into a polycation which then interacts with sodium CMC. Nearly quantitative precipitation can be achieved at low KCl concentration (ca. 0.005M) for a crown/carboxylate ratio of approximately 5, while for 0.1-0.2M KCl the precipitation is close to completion at a crown/CMC ratio of about 2. The precipitates solubilize again on addition of water or concentrated KCl. Precipitation also occurs with CsCl but not with NaCl. Potentiometric measurements were carried out to determine the complex formation constant of the three alkali ions to P18C6. Their values can be used to rationalize the observed phenomena. Charge equivalence appears to play an important role in the formation of the polysalt complexes.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1573-1581 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Macrocyclic polyether or crown ether ester derivatives of acrylic and methacrylic acid were synthesized and polymerized. The cation binding properties of the polymers determined by extraction of picrate salts were similar to those obtained for poly(crown ether)s derived from styrene. In the presence of a crown-complexable cation both polymers form insoluble polysalt complexes with sodium carboxymethylcellulose, potassium poly(styrene sulfonate), and potassium polyacrylate. The extent of precipitation depends on the type and concentration of cation as well as on the ratio polyanion to poly(crown ether). The precipitate appears to have an equal number of positive and negative charges. An insoluble hydrogen-bonded complex is formed in the absence of salt when poly(vinylbenzo-18-crown-6) and poly(acrylic acid) are mixed in 0.01M HCl. Organic solutes bound to the poly(crown ether)s, which occur in an aqueous mixture of poly(vinylbenzo-18-crown-6) and picrate anions, are precipitated with the poly(crown ether) when the polysalt complex is formed.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 61 (1962), S. 31-37 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Lack of termination in the “Living” polymer systems enables one to determine directly the absolute rate constant of propagation and of copolymerization. Anionic polymerizations in tetrahydrofuran are usually very fast, and a flow technique was developed to determine the rate of these reactions. The method is described and its use illustrated by studies on the following systems: styrene-p-methylstyrene, styrene-p-methoxystyrene, and styrene-2-vinylpyridine. The results indicate that the polarity of the reacting monomer is the dominant factor in determining the value of the copolymerization rate constant as long as the polarities of the monomers involved are similar. However, the results obtained on the system styrene-2-vinylpyridine clearly demonstrate that the terminal carbanion plays a major role when the polarities of the two monomers are very different. The technique can also be used to study the effect of the penultimate unit of a chain on the rate constant of propagation or copolymerization. Moreover, the chain length of the “living” polymer can be caried and its effect of the rate constant determined.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 108 (1967), S. 288-291 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A: General Papers 3 (1965), S. 3099-3106 
    ISSN: 0449-2951
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Anionic polymerization of vinylmesitylene was investigated in THF (counterion Na+) at temperatures ranging from +25° to -70°C. The homopropagation is slow (kp ∼ 11./mole-sec. at 25°C.), indicating the basically low reactivity of the monomer. Studies of conductivity and the retardation of the polymerization by the addition of Na+BPh4- demonstrate that free ions and ion pairs participate in the process. At 25°C. the kp of the free ion appears to be about 1000 times greater than that of ion pair. The outstanding feature of the polymerization is the proton transfer from the monomer to living end, producing an inert ion (or its isomer) which does not propagate. This reaction leads to retardation of the polymerization. Its contribution decreases on lowering the temperature, and the effect of Na+BPh4- indicates that the free ion, and not the ion-pair, acts as a base in the proton transfer.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Letters 2 (1964), S. 735-737 
    ISSN: 0449-2986
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 2219-2228 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetics of anionic copolymerization of styrene (S) and 1,1-diphenylethylene (D) were investigated in THF. The rate constant of addition of D to living polystyrene was found to be k1,2 ± = 250 l./mole-sec. for , Na+ ion-pair, and that for the free , Na+ ion is k1,2-∼400,000 l./mole-sec. Both values refer to 25°C. The addition of styrene to —D-, Na+ was found to be reversible: and k2,1 was determined by three different methods to be ∼0.5-0.7 l./mole-sec. Studies performed in a stirred-flow reactor led to k-21 = 13 sec. -1 and K21 ∼ 5 × 10-2 l./mole. An alternating copolymer is obtained in the presence of a large excess of 1,1-diphenylethylene.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Letters 3 (1965), S. 1037-1041 
    ISSN: 0449-2986
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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