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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 1111-1124 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal crosslinking and loss of vinyl unsaturation of syndiotactic 1, 2-polybutadiene(s-PB) at 180-230°C were prevented by stabilizers with 3, 5-di-t-butyl-4-hydroxybenzyloxy group. The s-PB samples (mp 140-198°C and MW 20,000-70,000) that contained the stabilizers could be melt-spun at a temperature below 220°C into 1-denier fibers to be used for the preparation of carbon fibers. The s-PB fibers with higher mp and/or higher MW could be obtained by the addition of a high boiling solvent such as tetralin. The relationship between the molecular structures of s-PB and the properties of resulting s-PB fibers, including the degree of molecular orientation measured by birefringence and x-ray diffraction, is presented. Spun fibers showed small swellings here and there along the fiber axis, which would have resulted from the inhomogeneity of the melt of s-PB spun at a temperature slightly above the melting point. The gelation was unlikely to occur.
    Additional Material: 8 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 21 (1983), S. 1853-1860 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Highly crystalline syndiotactic 1,2-polybutadiene (s-PB) having melting point (mp) up to 216°C was obtained by using a Co(acac)3-AIEt3-CS2 catalyst. The polymer with mp 208°C was found to have 99.7% 1,2 content and 99.6% syndiotacticity by 1H and 13C-NMR measurements. The s-PB can be molded by addition of a stabilizer such as 2,6-di-t-butyl-4-hydroxymethylphenol into fiber, film, and various shaped articles. The physical properties presented in the present article include stress-strain and dynamic mechanical behavior. The highly crystalline syndiotactic 1,2-polybutadiene was applied to a carbon fiber and UBEPOL VCR (cis-1,4-polybutadiene reinforced by fibrous syndiotactic 1,2-polybutadiene).
    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 21 (1983), S. 1951-1972 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Butadiene is polymerized by cobalt compound-organoaluminum-CS2 catalysts to give highly crystalline syndiotactic 1,2-polybutadiene (s-PB) having melting point up to 216°C. An aluminum-free catalyst, Co(C4H6)(C8H13)-CS2, is also effective. Syndiotactic polymerization with Co(C4H6)(C8H13)-CS2 is not interrupted by the addition of protic substances such as water and alcohol, but is influenced by donor or acceptor substances. The donor molecule, e.g., dimethylsulfoxide or dimethylformamide, decreases the stereoregularity, i.e., syndiotacticity and 1,2 content. An acceptor molecule of organoaluminum with appropriate acidity such as AlEt3-AlEt2Cl or tetraethylaluminoxane increases the molecular weight, stereoregularity, and yield of the polymer. In the presence of CS2 a mixture of cis-PB and s-PB was obtained by using Co(octoate)2-AlEt2Cl-H2O, with molar ratio H2O/Co less than unity. In the case of H2O/Co 〉 1, only cis-PB was obtained. By the addition of donor substances such as ester, ether, nitrile, and AlEt3, s-PB was obtained even when H2O/Co 〉 1. The amount and ratio of cis-PB and s-PB are dependent upon the nature and amount of the additives.
    Additional Material: 5 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 1973-1988 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 1H and 13C-NMR spectra of highly crystalline syndiotactic 1,2-polybutadiene (s-PB) are discussed in order to clarify the mechanism of butadiene polymerization with cobalt compound-organoaluminum-CS2 catalysts. Cis opening of the double bonds in the syndiotactic polymerization is affirmed by the study of the copolymer from perdeuteriobutadiene and cis,cis-1,4-dideuteriobutadiene. S-PB (mp 210°C) has 99.7% 1,2 units, 0.3% isolated cis-1,4 units, and 99.6% syndiotacticity. Polymer ends (2-methyl-3-butenyl group and conjugated diene structure) are also determined. The differences in free energy of activation between 1,2 and cis-1,4 propagation and between syndiotactic and isotactic propagation are 14.0 and 9.6 kcal/mol, respectively, for Co(acac)3-AlEt3-AlEt2Cl-CS2, and 6.7 and 5.7 kcal/mol, respectively, for the aluminum-free Co(C4H6)(C8H13)CS2 system. The conformation of s-PB in o-dichlorobenzene at 150°C is described by the sequence (tt)1.6(gg)(tt).
    Additional Material: 9 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 1989-1995 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A mechanism is proposed for the polymerization of syndiotactic 1,2-polybutadiene (s-PB) with soluble cobalt-organoaluminum-CS2. The proposed active species have structures which consist of side-on coordination of CS2 to cobalt, anti-π-allyl growing end, cisoid bidentate coordination of butadiene, and activation by complex formation with organoaluminum at the nonbonded sulfur of the coordinated CS2. This proposal is based on findings for the aluminum-free catalyst Co(C4H6)(C8H13)-CS2. It is tentatively interpreted that syndiotactic 1,2 polymerization proceeds under the influence of the side-on coordinated CS2, by which the reactivity between the terminal carbons of butadiene and the C3 of the π-allyl end is enhanced.
    Additional Material: 6 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 29 (1984), S. 1287-1296 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    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: AlEt3Cl was modified with TLTTP (trilauryltrithiophosphite) in the catalyst system consisting of TiCl3 and AlEt2Cl. The effects of TLTTP on the polymerization of propylene were studied in comparison with those of alkyl homologues of TLTTP. The catalytic behavior of the TiCl3-AlEt2Cl-TLTTP catalyst system in the polymerization of propylene was also studied in comparison with that of the TiCl3-AlEt2Cl catalyst system. In the study of the effect of various alkylthiophosphites added, it is found that the bulkiness of the alkyl group affects the rate of propylene polymerization and the stereoregularity of the resultant polymers. The TiCl3-AlEt2Cl-TLTTP catalyst system gave different catalytic behavior in the propylene polymerization from that of the unmodified conventional catalyst system (TiCl3-AlEt2Cl). These effects of TLTTP were considered to be due to the bulkiness of the alkyl groups attached to the phosphorous atom and the higher reactivity to TiCl3 of the modified AlEt2Cl than of the unmodified AlEt2Cl.
    Additional Material: 14 Ill.
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