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  • 1
    Electronic Resource
    Electronic Resource
    Effect of diffusion on rates and molecular weights in graft polymerization (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 623-643 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A theoretical analysis has been made of the graft polymerization process in terms of the quantitative interrelationship between the initiation rate Ri, the kp/kt1/ ratio of the monomer, the equilibrium solubility M of the monomer in the polymer, the polymer film thickness L, and the diffusivity D of the monomer in the polymer. It is shown how the values of these parameters in any grafting system interact to lead to diffusion-controlled graft polymerization. Whether graft polymerization is diffusion-free or diffusion-controlled depends on the values of Kp, d, kp/kp1/2, and L as gathered in the parameter A = [(Kp/kt1/2)Ri, D,/1/2] L/2. When the values of the various terms are such that A is less than 0.1 (i.e., D is large while Ri, kp, and L are small), the reaction is diffusion-free. When A is greater than 3 (i.e., D is small while Ri, kp, and L are large), the reaction is diffusion-controlled. The derived equations showing the relationship between kinetic and diffusional parameters are theoretically applicable to all grafting systems, i.e., for all monomer-polymer combinations under all conditions of reaction temperature, radiation intensity and polymer film thickness. The theoretical analysis has been verified for the rate and degree of polymerization for the radiation-induced graft polymerization of styrene to polyethylene.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.170130306
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  • 2
    Electronic Resource
    Electronic Resource
    Solution properties of poly acrylates. Part I. Poly(ethyl acrylates) and poly(n-propyl acrylates) (1967)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 107 (1967), S. 230-240 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Früher wurde beschrieben, daß das Anwachsen der Kettenlänge des Alkoholrestes in Estern der homologen Reihe von Polymethacrylaten die Eigenschaften dieser Verbindungen in Lösung beeinflußt. In der vorliegenden Arbeit wird über die Ergebnisse von Untersuchungen des osmotischen Druckes und über Lichtstreuungs- und Viskositätsmessungen von Polyäthyl- und Poly-n-propylacrylat in Methyläthylketon berichtet. Die Viskositäts- Molekulargewichts-Beziehung für die beiden Polymeren wurde aufgestellt. Die Konzentrationsabhängigkeit von [II/RTc] und [Hc/tau;] wurde bestimmt, die Ergebnisse wurden im Hinblick auf die Wechselwirkung von Polymeren und Lösungsmittel erörtert. Der Wechselwirkungsparameter χ und der mittlere Kettenendenabstand der polymeren Kette (r2)1/2 werden weitgehend durch die Wechselwirkung des α-Wasserstoffatoms des Polymeren einerseits und der Carbonylgruppe des Lösungsmittels andererseits beeinflußt. Wie aus der Theorie zu erwarten war, sinkt der zweite Koeffizient A2 mit dem Molekulargewicht, während der zweite Virialkoeffizient Γ2 steigt; die Koeffizienten A2Mw/[η] und Φ bleiben ziemlich konstant.
    Notes: Formerly it was reported that the length of the alcoholic residue of the homologous series of poly methacrylates affects their solution properties. In the present paper the results of osmotic pressure, light scattering, and viscosity measurements of poly(ethyl-) and poly-(n-propyl acrylate) in ethyl methyl ketone have been reported. The viscosity molecular weight relationship has been established for the two polymers. The concentration dependence of [II/RTc] and Hc/τ have been determined and the results have been discussed in light of polymer-solvent interaction. The interaction parameter χ and the root meansquare end-to-end distance of the polymer chain (r2)1/2 are largely influenced by the interaction between the α-hydrogen atom of the polymer and the carbonyl group of the solvent. As expected from theory the second coefficient A2 decreases and the second virial coefficient Γ2 increases with molecular weight and the coefficients A2Mw/[η] and Φ are fairly constant.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1967.021070122
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  • 3
    Electronic Resource
    Electronic Resource
    Cohesive-energy-densities of high polymers. Part VI. C.E.D. of polyvinyl esters (1965)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 84 (1965), S. 225-229 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Löslichkeitsparameter δ von Polyvinylacetat und -propionate wurden über die in einer Reihe von Alkylestern ausgeführten Messungen der Quellung und der Lösungsviskositäten bestimmt. Sie wurden mit den nach SMALL berechneten Werten verglichen. Die erhaltenen δ-Werte sind vergleichbar mit jenen der äquivalenten Strukturen, wohingegen in einer homologen Reihe δ mit waschsendem Volumen des alkoholischen Restes abnimmt.
    Notes: The solubility parameters (δ) of polyvinyl acetate and polyvinyl propionate were estimated by their swelling and solution viscosity measurements in a series of alkyl esters and were compared with the δ-values calculated from SMALL's result. The δ-values of these polymers are comparable with the δ-values of their structural equivalents, whereas in a homologous series δ decrease with increase in the volume of the alcoholic residue.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1965.020840120
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  • 4
    Electronic Resource
    Electronic Resource
    Cohesive energy density of high polymers. Part V. C. E. D. of polymethacrylates (1965)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 81 (1965), S. 173-179 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Kohäsionsenergiedichten von Methyl-, Äthyl-, Butyl- und Isobutylmethacrylasäureestern wurden über die Lösungsviskositäten in einer Reihe von Alkylestern bestimmt4,5. Die für die Polymeren erhaltenen Löslichkeitsparameter sind 9,40, 9,15, 9,00 und 8,65. Verglichen mit den Werten von Polyacrylsäureestern, sind diese Werte niedringer. Innerhalb der homologen Reihen nehmen die Kohäsionsenergiedichten mit zunehmender Länge der Alkoholketten ab.
    Notes: The C.E.D.'s of methyl, ethyl, butyl, and isobutyl methacrylates have been estimated from their solution viscosity measurements in a number of alkyl ester solvents,4,5. The solubility parameters obtained, (9.40, 9.15, 9.00, and 8.65) for the above polymers, suggest that C.E.D.'s of polymethacrylates are less than those of polyacrylates and in the homologous series, the C.E.D. decreases with increases in the length of the alcoholic chain.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1965.020810119
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  • 5
    Electronic Resource
    Electronic Resource
    Kinetics of polymerization of benzyl acrylate in bulk (1968)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 111 (1968), S. 168-171 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Reaktionskinetik der Polymerisation von Benzylacrylat bei 55, 60 und 65°C mit Azoisobuttersäuredinitril als Initiator wurde untersucht. Die Bruttopolymerisationsgeschwindigkeit, der Polymerisationsgrad, die Kettenübertragung durch das Monomere, das Verhältnis der Geschwindigkeitskonstanten fü Wachstum und Abbruch wurden berechnet. Die Bruttoaktivierungsenergie, die Differenz der Aktivierungsenergien für die Wachstums- und Abbruchsreaktion und der Frequenzfaktor wurden ebenfalls bestimmt.
    Notes: The kinetics of polymerization of benzyl acrylate has been studied at 55, 60, and 65°C with azobisisobutyronitrile as initiator. The overall rate of polymerization, degree of polymerization, chain transfer due to monomer, and the ratio of propagation and termination constant were calculated. The overall activation energy, the difference between the activation energy of propagation and termination, and the frequency factor are also reported.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1968.021110115
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  • 6
    Electronic Resource
    Electronic Resource
    An approach for estimating the permeation of phosphonofluoridates into a high polymer matrix part 1. Development of the approach (1987)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 27 (1987), S. 1338-1343 
    Details
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: An approach has been developed to estimate the solubility and diffusivity of toxic phosphonofluoridates in high molecular weight polymeric matrices based upon experimentation with nontoxic simulants. This approach is based on Gee's relation for estimating solubility (equilibrium swelling) from knowledge of the solubility parameters for the polymer and the simulant liquids concerned and on Van Krevelen's relation between diffusivity and activation energy of diffusion. The latter is interpolated from a standard plot of activation energy of diffusion against penetrant molar volume. Equilibrium swelling values and diffusivities for toxic alkyl phosphonofluoridates in styrene-butadiene rubber (SBR) and low density polyethylene (LDPE) were estimated from results of swelling measurements (as a function of time and at three different temperatures) involving the two polymers and a series of nontoxic liquids, similar to the toxic alkyl phosphonofluoridates.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760271711
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  • 7
    Electronic Resource
    Electronic Resource
    Cohesive-energy-density of high polymers. Part IV. C. E. D. of Polyacrylates (1963)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 67 (1963), S. 84-89 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Löslichkeitsparameter von Polyacrylsäuremethyl-, -äthyl-, -propyl- und -butylester wurden mittels Messungen ihrer Lösungsviskositäten in einer Reihe von Alkylestern als Lösungsmittel bestimmt. Die Ergebnisse stimmen gut mit jenen überein, die man über Quellungsmessungen erhielt. Es wurde beobachtet, daß in einer homologen Reihe die Kohäsionsenergiedichten mit zunehmender Kettenlänge des Alkohols abnehmen.
    Notes: The solubility parameters of polymethyl, -ethyl, -propyl, and -butyl acrylates were estimated by measuring their solution viscosities in a series of alkyl ester solvents. The results agreed well with those obtained by swelling measurements and it was observed that in the homologous series, c.e.d.8 decreases with increase in the alcoholic chain length.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1963.020670108
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  • 8
    Electronic Resource
    Electronic Resource
    Cohesive energy densities of high polymers. Part I. Determination of cohesive energy density from swelling measurements (1963)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 65 (1963), S. 29-38 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: An natürlichem Kautschuk, Polydimethylsiloxan, Hydropolybutadien und Polyurethan wurden mit zahlreichen flüssigen Verbindungen Quellungsmessungen ausgeführt. Die Berechnung der Löslichkeitsparameter dieser Polymeren erfolgte nach einer von GEE vorgeschlagenen Methode. Es wird eine kritische Sichtung vorgängiger Quellungsuntersuchungen vorgelegt. Daraus ergibt sich, daß hinsichtlich der unbefriedigenden Theorie der Lösung die Wahl der Lösungsmittel sehr wichtig ist, falls man Löslichkeitsparameter der Polymeren über vergleichende Quellungsmessungen ermitteln will.
    Notes: Swelling measurements with natural rubber, polydimethylsiloxane, hydropolybutadiene and polyurethane were made using a large number of liquids. The solubility parameters of these polymers were calculated, using the method suggested by GEE. A critical appraisal of the previous work on swelling has been reported. It is concluded that in view of the unsatisfactory position of the theory of solution, choice of solvents is very important while trying to estimate solubility parameter of the polymer from such comparative studies as swelling measurement etc.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1963.020650104
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  • 9
    Electronic Resource
    Electronic Resource
    Cohesive energy densities of high polymers. Part II. Cohesive energy densitites of polyacrylates and polymethacrylates from swelling measurements (1963)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 65 (1963), S. 39-46 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Kohäsionsenergiedichten (c.e.d.) mehrerer Polyacrylate und Polymethacrylate wurden durch Quellungsmessungen in einer Reihe von Alkylestern bestimmt. Die Werte für die Kohäsionsenergiedichten sind für die Polyacrylate höher als für die Polymethacrylate. In einer Art homologer Reihe nehmen die c.e.d.-Werte ab mit zunehmender Länge der alkoholischen Kette.
    Notes: The cohesive energy densities (c.e.d.) of a number of polyacrylates and polymethacrylates have been estimated by swelling measurements in a series of alkyl esters. It is seen that the magnitudes of c.e.d. for polyacrylates are higher than those for polymethacrylates and in a homologous series, c.e.d. decreases with increase in the length of the alcoholic chain.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1963.020650105
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  • 10
    Electronic Resource
    Electronic Resource
    Autoacceleration in polymerisation of acrylic esters. Part 1. Ethyl and n-propyl acrylate (1967)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 104 (1967), S. 125-134 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: In der vorliegenden Arbeit wird über Ergebnisse von Untersuchungen über die Selbstbeschleunigung der Polymerisation von Äthyl- und n-Propylacrylat berichtet. Die Arbeiten von BURNETT und DUNCAN werden einer kritischen Betrachtung unterzogen. Die Versuchsergebnisse werden der BURNETTschen Auffassung folgend gedeutet. Es wurde gefunden, daß mit abnehmender Initiatorkonzentration der kritische Umsatz, bei welchem die Selbstbeschleunigung beginnt, zunimmt. Ferner wurde gefunden, daß dieser bei gleichen Initiatorkonzentrationen stets für n-Propylacrylat größer ist, als für Äthylacrylat.
    Notes: In the present paper the results of the studies on the autoacceleration in polymerisation of ethyl and n-propyl acrylate are reported. The merits and demerits of both mechanisms proposed by BURNETT and DUNCAN have been critically discussed and the results have been interpreted, following BURNETT et al. It has been observed that the critical degree of conversion where the autoacceleration starts, increases with the decrease of the initiator concentration; for any particular concentration of the initiator it is higher for n-propyl acrylate than for ethyl acrylate.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1967.021040113
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