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  • 1
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The low temperature polymerization of isobutene with AlCl3 in methyl chloride solutions has been investigated. In a series of experiments the degree of polymerization of poly(isobutene)as a function of monomer concentration has been determined. It was found that increasing amounts of methyl chloride causes a marked increase in molecular weight until a sharp maximum is reached at about 0.10 mole fraction isobutene. Further dilution causes a precipitous drop in the molecular weights. It has been shown that increase in dielectric constant does not account for the rise in degree of polymerization. The log of degree of polymerization was found to be inversely proportional to the log of catalyst concentration between about 10-3-10-2 wt.-% (7.53 × 10-5-10-4 mole liter-1)AlCl3 on monomer. At higher catalyst concentrations the degree of polymerization becomes concentration independent. This was true for methyl isobutene-chloride systems containing 1.0, 0.65, and 0.25 mole fraction of monomer. The product degree of polymerization times monomer concentration falls on the same curve.
    Additional Material: 4 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 49 (1961), S. 189-202 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relation existing between monomer concentration and degree of polymerization of polyisobutenes obtained in various diluents with AlCl3 catalyst has been investigated at -78°C. Methyl chloride, ethyl chloride, methylene chloride, vinyl chloride, and n-pentane were used as diluents. It was demonstrated that the DP increases with decreasing monomer concentration irrespective of the investigated polymerization medium. A hypothesis which could explain the experimental facts is presented. The influence of dielectric constant on the molecular weight of polyisobutene has been studied in methyl chloride - carbon disulfide mixtures. The seeming contradiction existing between experimental findings and expectation based on older theories has been resolved by the introduction of “effective D.C.” theory. The “lifetime” of carbonium ions and the “temperature build-up” in the fast low-temperature polymerization has been estimated.
    Additional Material: 7 Ill.
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  • 3
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The low-temperature AlCl3-initiated polymerization of isobutene has been investigated. Direct evidence of the occurrence of chain-breaking reactions is presented. The polymer molecular weight can be affected by changes in reaction temperature between -35 and -78°C. at the same conversion level. The discovery of inversion temperature (Ti) is described. At Ti, the molecular weight becomes independent of monomer concentration. We call Ti the temperature level at which the dependence of product molecular weight on the monomer concentration changes its sign. The inversion temperature has been observed in methyl chloride, ethyl chloride, and vinyl chloride, and vinyl choride diluents. A theory explaining the phenomenon is postulated. It is suggested that competing chain breaking process having dissimilar activation energies determine the molecular weight. Their effects cancel each other at Ti. The previously reported, unusual inverse relation existing between molecular weight and monomer concentration is explained by the concept of Ti.
    Additional Material: 8 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 64 (1963), S. 1-9 
    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 kationische Tieftemperaturpolymerisation von 3-Methylbuten-1 wurde untersucht. Zwei kristalline Modifikationen (α und β) wurden durch RÖNTGENdiagramme charakterisiert. Die „d“-Abstände sind (i.Å): 1,8, 5,4, 4,6, 2,8, 2,4, 2,1 für die α-Form und 9,0, 5,4, 4,8, 3,6, 2,8, 2,1 für die β-Form. Die α-Form ist orientiert, und die Identitätsperiode in der c-Richtung ist 1,8 Å; dies deutet auf 2 Grundeinheiten in der Einheitszelle. Die α-Modifikation ist stabiler als die β-Form, d.h. wenn β-Proben aus Lösung umgefällt wurden, erhielt man die α-Form.
    Notes: The low temperature cationic polymerization of 3-methyl butene-1 was studied. Two crystalline polymer modifications (α und β) were characterized by their X-ray diffraction patterns. The “d” spacings of the α and β forms are (in Å): 7.8, 5.4, 4.6, 2.8, 2.4, and 2.1; and 9.0, 5.4, 4.8, 3.6, 2.8, and 2.1, respectively. The α modification was oriented and the repeat distance in the “c” direction is 7.8 Å. This indicates 2 structural units in the repeat unit. The α modification is more stable than the β form e.g., when β specimens were reprecipitated from solutions the α form was obtained.
    Additional Material: 1 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 45 (1960), S. 229-229 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 6
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 46 (1960), S. 233-243 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The homophase polymerization of isobutene in pentane solution with AlCl3 catalyst solutions has been studied at -78°C. The DP of isobutene increases with increasing amounts of pentane present. Below about 10% monomer content the polymerization is completely homogeneous. The reaction is extremely fast, and conversions and molecular weights do not change after the introduction of catalyst. Only when more catalyst is added can the reaction proceed to higher conversions. A linear relation exists between conversion and catalyst concentration. The dependence of DP or the conversion has been established. The differential DP's increase until a well defined maximum is reached at low conversions. At higher conversions the DP starts to decay sharply. A hypothetical termination mechanism has been proposed.
    Additional Material: 4 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 45 (1960), S. 227-228 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 53 (1962), S. 28-32 
    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 Polymerisation von 3-Methylbuten-1 wurde in Gegenwart von Aluminiumtrichlorid-Lösungen bei tiefen Temperaturen untersucht. Ein kristallines hochpolymeres Produkt wurde bei -130°C erhalten; seine physikalische Charakterisierung wird beschrieben. Das Röntgenbeugungsdiagramm dieses neuen kristallinen Polymeren unterscheidet sich von dem des isotaktischen Poly(3-Methylbuten-1), das in Gegenwart von Metallalkyl-Koordinationskatalysatoren erhalten wurde. Ein möglicher Molekülbau wird besprochen.
    Notes: The polymerization of 3-methyl butene-1 was studied using AlCl3 solutions at low working temperatures. A crystalline high polymer was obtained at -130°C. Physical characterization of this product is reported. The X-ray diffraction pattern of this new crystalline polymer is different from that of isotactic poly(3-methyl butene-1) obtained with metal alkyl coordination catalyst. A tentative structure is discussed.
    Additional Material: 2 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A: General Papers 1 (1963), S. 331-346 
    ISSN: 0449-2951
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Further studies with the isobutene-aluminum chloride-methyl chloride system has led to a better understanding of the dependence of degree of polymerization on monomer concentration and on temperature. Polymerizations were also carried out in C14-labeled methyl chloride to determine solvent incorporation in the polymer. A quantitative kinetic theory has been developed which explains the behaviour of the isobutene-aluminum chloride system in polar solvents such as methyl chloride, vinyl chloride, and ethyl chloride. The rate-determining step in propagation is polymer activation, presumably by ion separation. The DP of the polymer is determined principally by two competing chain-breaking processes; namely, chain transfer to monomer and/or chain breaking involving the solvent. The latter reaction becomes important in polar solvents at higher temperatures. The influence of phase separation has also been studied. The results indicate that the polymer molecule precipitates after it has under gone either a chain breaking or a chain termination reaction.
    Additional Material: 6 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A: General Papers 2 (1964), S. 367-380 
    ISSN: 0449-2951
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The cationic polymerization of 3-methylbutene-1 was investigated with the use of aluminum chloride and aluminum bromide initiators in the temperature range of -62 to -102°C. Polymerizations are homogeneous in the presence of pentane, and above -50°C. in methyl chloride. However, the polymer tends to precipitate below -50°C. in methyl chloride. The molecular weight of poly-3-methylbutene-1 increases with decreasing temperatures at the same conversion level. Significantly, the molecular weights increase with conversion and seem to reach their maximum at high conversions. Higher molecular weights were obtained in n-pentane-alkyl chloride mixtures than in methyl chloride solution alone. The molecular weights are independent of catalyst concentrations in the range investigated (31.8-7.97 × 10-4 mole/l. AlBr3 and 57.6-28.8 × 10-4 mole/l. AlCl3). The rate of homogeneous polymerization with aluminum bromide in propane solvent was studied. The rate is first order in monomer concentration and catalyst concentration and the rate constant is 0.610 l./mole sec. The apparent activation energy calculated from the Arrhenius plot is 6.57 kcal./mole. In methyl bromide the rate of polymerization increases significantly (effect of the dielectric constant). In toluene the molecular weight as well as the rate is strongly depressed indicating the preponderance of a chain breaking mechanism involving this solvent.
    Additional Material: 9 Ill.
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