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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Polymer International 34 (1994), S. 23-33 
    ISSN: 0959-8103
    Keywords: polyesters ; diacetylenes ; cross-polymerisation ; DSC ; Raman spectroscopy ; tensile deformation ; Raman shift factors ; 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: A series of diacetylene-containing polyesters with number-average molar masses (GPC) in the range 900-4200 g mol-1 were prepared from terephthaloyl chloride and hexa-2,4-diyne-1,6-diol using benzoyl chloride as a monofunctional reactant for control of molar mass. Degrees of crystallinity were estimated from WAXD to be up to 29%. Correlations between molar mass, melting behaviour, degree of crystallinity and thermal cross-polymerisation of diacetylene-containing polyesters have been established using hot-stage microscopy, DSC and resonance Raman spectroscopy. The polyester with M̄n of 1264 g mol-1 gave the best balance between processability and the ability to cross-polymerise efficiently. Its degree of crystallinity before cross-polymerisation was estimated from WAXD measurments to be 24%, a value coincident with the percentage conversion of diacetylene units to polydiacetylene chains measured by 13C solid-state NMR. The optimum conditions for compression moulding the polyester to produce a material with a strong Raman spectrum involved heating under vacuum at 120°C for 6h after an initial 3 h heat-up period. The material thus produced gave an intense Raman C=C stretching band, which upon tensile deformation shifted linearly with strain to lower wavenumber by 12.0 cm-1 %-1. The potential use of the diacetylene-containing polyesters in the preparation of model blends for use in quantitative micromechanics studies of stress transfer between phases is briefly discussed.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 31 (1986), S. 1963-1975 
    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: A range of hydroxy-terminated polymyrcenes has been prepared using hydrogen peroxide initiated polymerization of pyroysate grade, β-myrcene in n-butanol solution at 100°C. An oligomeric fraction, containing a large proportion of dimeric material formed via the Diels-Alder reaction, always accompanies the major polymeric fraction. Procedures are described for the removal of this oligomeric material. Polyols so prepared and purified had number average molecular weights (Mn) between 4000 and 2000 g mol-1 at low and high initiator concentrations, respectively, with corresponding number average functionalities (fn) between 1.3 and 2.3 and polydispersities (Mw/Mn) of ∼1.3. The microstructure of the polyols was investigated using NMR spectroscopy from which the main mode of propagation during polymerization of myrcene was deduced to be 1,4 addition across the conjugated double bonds. Glass transition temperatures of the polymyrcenes measured by differential scanning calorimetry were in the range -50-60°C.
    Additional Material: 10 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 33 (1987), S. 1445-1446 
    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
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 31 (1986), S. 1549-1565 
    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: Two hydroxy-functionalized liquid rubbers, one a commercially available polybutadiene (PB) and the other a specially synthesized polymyrcene (PM), have been converted into homopolyurethane elastomers by reaction with 4,&4prime;-diphenylmethane diisocyanate (MDI). Additionally, PB and PM, each in admixture with various amounts of 1,4-butane diol, were reacted with MDI to yield two series of segmented copolyurethanes having different hard-block contents (0-30% w/w). The physical properties of these elastomers have been compared by stress-strain, thermal, and dynamic mechanical analyses, and by swelling experiments. The two series of segmented copolyurethanes have similar morphologies being almost completely phaseseparated and variations in physical properties have been empirically related to hard block contents. The PM-based elastomers exhibited higher Tg values, ultimate elongations, and larger swelling ratios, but were softer and possessed lower tensile strenghts in comparison with elastomers based on PB. These differences have been related to solfraction contents, the nature and distribution of molecular species present in the parent liquid rubbers and hence to polyol functionalities (f̄n). Analysis of the stress-strain data from the homopolyurethanes using the Mooney-Rivlin expression enabled the relationship between f̄n and elastomer structure to be quantified in terms of the molar mass (M̄c) of the polyurethane network chains forming the soft blocks.
    Additional Material: 8 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 33 (1987), S. 997-998 
    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
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 33 (1987), S. 2217-2229 
    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: A range of hydroxy-terminated polymyrcenes has been prepared using hydrogen peroxide initiated polymerization of pyrolysate grade, β-myrcene in n-butanol solution at 100°C. An oligomeric fraction, containing a large proportion of dimeric material formed via the Diels-Alder reaction, always accompanies the major polymeric fraction. Procedures are described for the removal of this oligomeric material. Polyols so prepared and purified had number average molecular weights (Mn) between 4000 and 2000 g mol-1 at low and high initiator concentrations, respectively, with corresponding number average functionalities (fn) between 1.3 and 2.3 and polydispersities (Mw/Mn) of ∼ 1.3. The microstructure of the polyols was investigated using NMR spectroscopy from which the main mode of propagation during polymerization of myrcene was deduced to be 1,4 addition across the conjugated double bonds. Glass transition temperatures of the polymyrcenes measured by differential scanning calorimetry were in the range -50--60°C.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 33 (1987), S. 2231-2248 
    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: Two hydroxy-functionalized liquid rubbers, one a commercially available polybutadiene (PB) and the other a specially synthesized polymyrcene (PM), have been converted into homopoly-urethane elastomers by reaction with 4,4′-diphenylmethane diisocyanate (MDI). Additionally, PB and PM, each in admixture with various amounts of 1,4-butane diol, were reacted with MDI to yield two series of segmented copolyurethanes having different hard-block contents (0-30% w/w). The physical properties of these elastomers have been compared by stress-strain, thermal, and dynamic mechanical analyses, and by swelling experiments. The two series of segmented copolyurethanes have similar morphologies being almost completely phase-separated and variations in physical properties have been empirically related to hard block contents. The PM-based elastomers exhibited higher Tg values, ultimate elongations, and larger swelling ratios, but were softer and possessed lower tensile strengths in comparison with elastomers based on PB. These differences have been related to sol-fraction contents, the nature and distribution of molecular species present in the parent liquid rubbers and hence to polyol functionalities (fn). Analysis of the stress-strain data from the homopolyurethanes using the Mooney-Rivlin expression enabled the relationship between fn and elastomer structure to be quantified in terms of the molar mass (Mc) of the polyurethane network chains forming the soft blocks.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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