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  • 1
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1691-1702 
    ISSN: 0887-624X
    Keywords: grafting ; basic functionalization ; free radical polymerization ; methacrylate ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The grafting of 2-(dimethylamino)ethyl methacrylate (DMAEMA) onto two model hydrocarbons, squalane and n-eicosane, and to linear low density polyethylene (LLDPE) has been investigated. The results of the study indicate that a high reaction temperature, 160°C, and a low concentration of monomer, less than 0.3 M, are optimum conditions for the grafting reaction. Reaction products, which consisted of grafted hydrocarbons and poly(DMAEMA), were separated by solvent extraction and vacuum distillation; samples were then analyzed by NMR and FTIR spectroscopy and size exclusion chromatography. 1H-NMR spectroscopy indicates that grafted squalane contained approximately 6 DMAEMA units per squalane residue. 1H- and 13C-NMR and molecular weight studies strongly suggest that the grafts onto the model hydrocarbons consist of single DMAEMA units. Results of the melt grafting of DMAEMA onto LLDPE show that the grafting efficiency and degree of grafting are substantially lower than were expected from the model system. © 1994 John Wiley & Sons, Inc.
    Additional Material: 11 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 641-651 
    ISSN: 0887-624X
    Keywords: cascade polymers ; dendritic polymers ; arborols ; dendrimers ; starburst polymers ; nomenclature ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cascade (dendritic) polymers are discrete, highly branched, monodisperse polymers that possess branching patterns described by a mathematical progression. A systematic nomenclature that accurately represents these molecules is described. © 1993 John Wiley & Sons, Inc.
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 1589-1600 
    ISSN: 0887-624X
    Keywords: reactivity ; amines ; functional polymers ; anhydride ; carbonxylic acid ; crosslink ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactive melt processing of different types of diamines with polyethylene containing carboxylic acid groups and polystyrene containing anhydride groups was carried out. The reactivity of primary, secondary, and tertiary diamines with these acid polymers was determined using various techniques. Molecular weight increases due to crosslinking were observed through (1) changes in the torque during the reactive processing, (2) decrease in melt flow indices, and (3) decrease in solubility of the reaction products. The chemical compositions of the reaction products were examined by Fourier transform infrared (FTIR) spectroscopy. Thermal analysis using differential scanning calorimetry (DSC) was carried out to determine the crystallization behavior, glass transition temperatures, and thermal stabilities of the reaction products. Results show that the primary amine is the most reactive towards carboxylic acid or anhydride groups followed by the secondary and then the tertiary amine. Anhydride groups on polymers are of higher activity towards secondary or primary amino groups than carboxylic acid groups in the nucleophilic acyl substitution reactions. Reaction products crosslinked with the primary diamine are less stable than their parent acidic polymers. On the other hand, crosslinking with the secondary or tertiary diamine gives products with higher thermal stability than the parent acidic polymers. The formation of reversible and irreversible crosslinks with different types of diamines is also reported. © 1992 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 41 (1990), S. 2285-2300 
    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: The grafting of maleic anhydride (MAn) to low density polyethylenes (PEs) dissolved in 1,2-dichlorobenzene (DCB) has been studied. Grafting was successful at temperatures of about 160°C both in air without initiator and under nitrogen with the radical initiator 2,5-di(t-butylperoxy)-2,5-dimethyl-3-hexyne (LPO). The presence of succinic anhydride grafts was shown by FTIR spectroscopy of the product; 1H-NMR spectroscopy indicates that the grafts consist of single succinic anhydride units. The graft content was determined by nonaqueous titration, and the extent of crosslinking inferred from the melt flow rates (MFR) of the products. The effects of concentration of initiator, MAn, and PE on the graft content were determined; the influence of PE structure, reaction time, and temperature was also studied. Melt blending of the grafted PE with polystyrene containing oxazoline functional groups (OPS) was investigated using a Rheomix mixer. The interpolymer reaction which occurs during blending was studied by means of FTIR, and the morphology of the blends by scanning electron microscopy (SEM). Information was also gained from the change in torque viscosity during the blending process.
    Additional Material: 12 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 44 (1992), S. 2167-2177 
    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: Blends of a styrene-maleic anhydride copolymer (SMA) with polyethlene (PE) or polyethylene melt grafted with tertiary (PE-g-DMAEMA) or secondary (PE-g-tBAEMA) amino methacrylate were prepared by blending in a batch melt mixer. The morphology of these blends at various compositions was examined with a scanning electron microscope (SEM) and related to their tensile and impact properties. The SMA/PE blends are found to have the typical coarse morphology of incompatible blends and poor mechanical properties, while their reactive conterparts, SMA/PE-g-DMAEMA or SMA/PE-g-tBAEMA blends, show finer morphology and modestly improved tensile and impact strength. This was attributed to chemical interaction of the acidic anhydride and the basic amino groups. The greater improvement in morphology for SMA/PE-g-tBAEMA than for SMA/PE-g-DMAEMA suggests a stronger interaction between the secondary amino groups and the anhydride groups, possibly with the formation of SMA-g-tBAEMA-g-PE graft polymer through amide covalent bonds. The amide formation appears to occur at the interfacial region in the blends and is too little to be detected by Fourier transform infrared (FTIR) spectra. However, differential scanning calorimeters (DSC) and the viscosity measurements indicate crystallinity and molecular weight changes for the SMA/PE-g-tBAEMA blends, supporting an argument for the formation of SMA-g-tBAEMA-g-PE grafts at the phase interface.
    Additional Material: 8 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 52 (1994), S. 783-788 
    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: Hydrogles, sensitive to pH, were prepared by copolymerizing 2-hydroxyethyl methacrylate (HEMA) with 2-dimethylaminoethyl methacrylate (DMA). The mole fraction of the DMA monomer present during synthesis was fixed at 0.3, while the volume fraction of total monomer varied from 0.29 (I) to 1.0 (II). Swelling equilibria were measured in citrate of phosphate buffer for pH from 3.0 to 7.6 Swelling of the hydrogels depends on the volume fraction monomer present during synthesis, solution, pH, and identity of the buffer, Hydrogel I reached a four-fold larger swelling ratio (g swollen hydrogel/g dry hydrogel) in pH 3.0 citrate buffer, as compared to hydrogel II. Experimental results are interpreted on the basis of ideal Donnan equilibria. © 1994 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 39 (1990), S. 655-678 
    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: Polystyrene (PS) and polyethylene (PE), along with their reactive counterparts, i.e., polystyrene having oxazoline reactive groups (OPS) and polyethylene with carboxylic acid groups (CPE), were melt blended in a Rheomix mixer. These blends were prepared by mixing these polymers in various proportions under a variety of conditions. In an alternate procedure the OPS, CPE graft polymer (OPS-g-CPE) was prepared by melt blending these two polymers beforehand, and subsequently this grafted polymer was used as a compatibilizer for PS-PE blends. The effects of the addition of OPS and CPE, on the one hand, and OPS-g-CPE, on the other hand, on the compatibility of PS-PE blends were investigated. The morphology of these blends was examined with a scanning electron microscope (SEM) and related to their tensile properties. The PS-PE blends are found to have the typical coarse morphology of incompatible blends and poor tensile properties while their reactive counterparts, OPS-CPE blends, have fine grain microstructure and show improved tensile strength throughout the range and improved elongation in the PE-rich blends. Relatively low concentrations of the reactive pair, oxazoline and carboxylic acid, are shown to be necessary to produce improved compatibility. The preblended graft copolymer OPS-g-CPE imparts compatibility to PS-PE blends also but not as effectively. This suggests that the addition of OPS and CPE during melt mixing of PS and PE forms OPS-g-CPE polymer at the interface and that these ingredients act as “in situ reactive compatibilizers” which improve physical properties.
    Additional Material: 10 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 41 (1990), S. 1299-1313 
    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: Functionalization of molten linear low-density polyethylene (LLDPE) with 2-(dimethylamino)ethyl methacrylate (DMAEMA) was studied in an intermeshing co-rotating twin-screw extruder using a peroxide initiator. The influence of monomer concentration, initiator concentration, reaction temperature, the screw speed, and the mean reaction residence time on the grafting reaction was investigated in order to determine the reaction conditions necessary to obtain a controlled degree of grafting, DG, while minimizing homopolymerization and crosslinking. Relatively high grafting levels can be obtained without excessive polyethylene crosslinking by using high monomer concentrations, wm, with low initiator concentrations, wI. DG increased with increasing monomer concentration when wm exceeded a certain value. Processing temperatures between 130 and 160°C are optimal to achieve high grafting efficiency, GE. Too high a processing temperature resulted in both low DG and GE. An optimal reaction residence time of about 5 min was found for wm = 23 wt % and wI = 0.56 wt % to obtain relatively high DG and GE. The melt flow index of the reaction product, MFI, increased with increasing wm at constant wI. This suggests that the DMAEMA monomer has the ability to suppress crosslinking of the LLDPE chains. The ability of the DMAEMA monomer to compete for initiator and polymer radicals and reduce LLDPE crosslinking was further demonstrated by the study of sequential addition of monomer and initiator along the extruder. The competition among the three reactions (i.e., the desired grafting, homopolymerization, and crosslinking) is discussed.
    Additional Material: 7 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 48 (1993), S. 1199-1208 
    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: Using organic peroxide initiators in the melt grafting of monomers containing amino groups onto polyethylenes is known to cause serious discoloration of the resulting polymers. To eliminate the discoloration while preserving the controlled degree of grafting, a nonoxidative and hydrogen-abstracting initiator with appropriate thermal stability is needed. In this study, the hydrogen-abstracting capability of three azo initiators with suitable decomposition rates in the melt grafting temperature ranges was evaluated using polyethylene cross-linking and polypropylene degradation experiments (called “hydrogen-abstracting experiments”). Among the three azo initiators tested, only a phenylazo initiator, 2 - phenylazo - 2,4 - dimethyl - 4 - methoxyl - valeronitrile (V-19), demonstrated strong hydrogen-abstracting capability from polymer backbones. These three azo initiators were used in the melt grafting of 2 - (N, N - dimethylamino) ethyl methacrylate (DMAEMA) and 2-(N-t -butylamino) ethyl methacrylate (tBAEMA) onto a linear low-density polyethylene (LLDPE). In agreement with the results obtained from the hydrogen-abstraction experiments, only V-19 led to a considerable amount of grafting of both DMAEMA and tBAEMA onto LLDPE. As expected, polymers grafted with V-19 showed significantly reduced discoloration compared with those grafted with peroxide initiators. Further examination of the grafting results indicated that the initiator efficieny, defined as the number of grafted monomer units per radical generated from initiator decomposition, was higher with the phenylazo initiator than with peroxide initiators. The hydrogen-abstracting capability of the phenyl free radical generated from the decomposition of V-19 was estimated to be higher than peroxide and methyl free radicals produced in the decomposition of peroxide initiatros. © 1993 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 13 (1969), S. 369-376 
    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: Polyvinylpyrrolidone and dextran polysaccharides have been fractionated by ultrafiltration by using newly developed membranes with sharp molecular weight cutoffs. Three different experimental techniques were employed: (a) batch ultrafiltration by using progressively more retentive membranes; (b) continuous ultrafiltration by using several similar membranes in series; (c) variable pressure ultrafiltration by using a single membrane and varying the applied pressure. Ultrafiltration is shown to be a technique of preparative fraction having the advantages of simplicity, speed, and economy.
    Additional Material: 5 Ill.
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