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  • Articles: DFG German National Licenses  (26)
  • Electronic Resource  (26)
  • 1990-1994  (9)
  • 1970-1974  (11)
  • 1960-1964  (6)
  • 1890-1899
  • Polymerization
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  • Articles: DFG German National Licenses  (26)
Material
  • Electronic Resource  (26)
Years
Year
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of molecular evolution 38 (1994), S. 433-437 
    ISSN: 1432-1432
    Keywords: Aziridine ; Polymerization ; Template polymerization ; Oligonucleotide initiators ; Electrophoretic analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract We have prepared a [32P]-labeled oligonucleotide probe carrying a free primary amine at its 3′terminus. This probe is used to initiate polymerization of aziridine (ethyleneimine) in aqueous solution. The nature of the oligomeric products and the kinetics of their formation are then monitored by gel electrophoresis. Our results are generally consistent with those obtained using conventional techniques. We have also investigated the effect of polyanionic templates on the rate of oligomerization of aziridine. We find that water-soluble polyanions generally accelerate the polymerization. The sodium salt of polymethacrylic acid is the most effective of the templates that we studied. The methods introduced in this paper should be applicable to a variety of polymerization reactions in aqueous solution. They should greatly simplify the screening of potentially prebiotic polymerization reactions.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Cellular and molecular life sciences 49 (1993), S. 110-117 
    ISSN: 1420-9071
    Keywords: Polymerization ; sickle hemoglobin ; sickle cell disease ; kinetics ; thermodynamics ; polymer domains ; nucleation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract The polymerization of sickle hemoglobin occurs by the same mechanisms in solutions and in cells, and involves the formation of 14 stranded fibers from hemoglobin molecules which have assumed a deoxy quaternary structure. The fibers form via two types of highly concentration-dependent nucleation processes: homogeneous nucleation in solutions with hemoglobin activity above a critical activity, and heterogeneous nucleation in similarly supersaturated solutions which also contain hemoglobin polymers. The latter pathway is dominant, and creates polymer arrays called domains. The individual polymers bend, but also cross-link, and the resulting mass behaves as a solid. The concentration of polymerized hemoglobin increases exponentially unless clamped by rate limiting effects such as oxygen delivery.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1435-1536
    Keywords: Polymerization ; oligomerization ; norbornene ; PdCl2 catalysis in water ; emulsions ; latex ; 13C NMR ; tacticity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Polymerization of norbornene using PdCl2 as catalyst is generally carried out at high temperatures in the absence of solvent. Low yields of polymer with relatively undefined molecular weights are obtained under these conditions. We describe the first example of polymerization of norbornene in water dispersion or aqueous emulsions catalyzed by PdCl2. Good yields of polymers and oligomers were obtained. Furthermore, in aqueous emulsions, novel microlatex which cannot be obtained by radical or ionic routes were synthesized, with particles sizes (≈10 nm.) generally only observed in microemulsion polymerizations. The stereochemistry of the polymers of low molecular weight was partially elucidated by13C NMR.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1573-5133
    Keywords: Acidification ; Al-chemistry ; Speciation ; Polymerization ; Al-toxicity ; Freshwater fish
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Synopsis The present study focuses on the effect of temperature on Al-chemistry and the subsequent toxicity to smoltifying Atlantic salmon, Salmo salar. Fish were exposed to acidic Al-rich water at different temperatures, and mortality, ventilation frequency and various blood parameters were measured. The relationship between temperature and Al-toxicity was documented as mortality increased systematically with increasing temperature. Physiological disturbances at the gills reflected the temperature dependent Al-toxicity. The temperature dependent toxicity observed is probably due to the degree of ongoing Al-polymerization.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Polymers for Advanced Technologies 4 (1993), S. 435-438 
    ISSN: 1042-7147
    Keywords: Ziegler-Natta ; Catalyst ; Polymerization ; Ethylene ; Styrene ; Copolymers ; 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
    Notes: The magnesium chloride supported Ziegler-Natta catalysts are able to copolymerize ethylene and styrene in conditions of high activity. Different parameters, including catalyst type, monomer ratio, temperature and Lewis bases, allow variation of the activity and reactivity ratio. The incorporation of styrene in the copolymer remains always rather limited in moles. The products obtained contain less than 20% styrene in weight, and seem very similar in structure to linear low-density polyethylenes (LLDPE) obtained with the same catalyst: the melting temperature is only about 5°C lower than that of pure polyethylene. The polymer can be fractionated by solvents in a similar manner to LLDPE, and contains a styrene-enriched fraction, but homopolystyrene production has never been observed.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Polymers for Advanced Technologies 4 (1993), S. 415-422 
    ISSN: 1042-7147
    Keywords: Polymerization ; Metallocenes ; Aluminoxane ; Metal-filled polymers ; 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
    Notes: Homogeneous catalysts based on metallocenes/methylaluminoxane are totally absorbed on surfaces of different metals. Because the methylaluminoxane is relatively stable against small molecules such as water covering metal surfaces, the aluminoxane can be fixed on powders without losing its activity. After treatment with the metallocene, active sites are only formed on the surface of the fillers. Upon injection of the olefins they are polymerized in the presence of the metals. Olefins such as ethene and propene, and cycloolefins or dienes, are used.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Polymers for Advanced Technologies 4 (1993), S. 406-414 
    ISSN: 1042-7147
    Keywords: Polyolefin ; Polypropylene ; Polyethylene ; Catalyst ; Polymerization ; Process ; Elastomer ; 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
    Notes: The polyolefins, especially polypropylene and polyethylene, industry of today is very different from that of 10 years ago. The development of highly active and stereospecific catalysts, represented by Ti/Mg supported catalysts, have made the gas-phase polymerization process practical.The trend in catalyst development is shifting from an emphasis on improving the stereospecificity and activity toward improving the polymer physical properties, processability and morphology.Many hybrid thermoplastic olefins, such as high-impact copolymers, propylene-ethylene-butene terpolymers, and very low density polyethylene, have already been developed by utilizing the features of the gas-phase polymerization process.These hybrid thermoplastic olefins cover a very broad range of products. They cannot be clearly identified as polyethylenes, polypropylenes or elastomers.Incidentally, metallocene catalysts for polyolefins have been under development for the past 15 years, and are now in the early stage of commercialization. These catalysts differ significantly from the conventional heterogeneous catalysts.They can polymerize not only ethylene, propylene and other linear α-olefins, but also styrene, cycloolefins and functional monomers In addition, they can control the microstructure of polymer molecules by varying the transition metals and the cyclopentadienyl ligands.Because of these features, we have to be confident that the development of metallocene catalysts, or more widely homogeneous catalysts, may be a dominant force throughout the 1990s in the polyolefin industries.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 2691-2695 
    ISSN: 0009-2940
    Keywords: fac-[Ru(O2CCH3)2(PPh3)3] · 2 CH3CO2H ; Tris(triphenylphosphane)ruthenium(II) ; Polymerization ; Bicyclo[2.2.1]hept-2-ene ; Ruthenium complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: [Ru2(μ-O2CCH3)4(O2CCH3)] reacts with excess triphenylphosphane in acetic acid to give fac-[Ru(O2CCH3)2(PPh3)3] · 2CH3CO2H (1), which crystallizes in the triclinic space group P 1- with Z=2. The three phosphane ligands are in the sterically congested facial configuration, and the distorted octahedral geometry around the metal is completed by a unidentate and chelating acetate. A variable temperature 31P{1H}-NMR study of the complex in CH2Cl2 showed the three phosphanes to be inequivalent at low temperature. On raising the temperature two separate coalescence processes are observed, ultimately making all of the phosphanes equivalent at room temperature. Complex 1 shows slight catalytic activity for the ring-opening polymerization of bicyclo[2.2.1]hept-2-ene (norbornene).
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Polymers for Advanced Technologies 2 (1991), S. 21-24 
    ISSN: 1042-7147
    Keywords: Polymerization ; Curing ; Laser ; Acrylic Monomer ; Ultraviolet Curing ; 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
    Notes: Photopolymerization of multifunctional acrylic monomers using excimer and Nd: YAG lasers operated at five different UV wavelengths is reported. The effects of different wavelengths on the surface and bulk cure both in air and under argon are investigated and discussed.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Journal of molecular evolution 3 (1974), S. 115-120 
    ISSN: 1432-1432
    Keywords: Adenosine Cyclic 2′, 3′-Phosphate ; Polymerization ; 1, 2-Diaminoethane ; Oligonucleotides ; Prebiotic ; Gel Permeation ; Ion Exchange
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Adenosine cyclic 2′, 3′-phosphate has been polymerized at room temperature in the dry state using 1, 2-diaminoethane at alkaline pH as catalyst. The high molecular weight products have been analyzed by several different methods, including ion exchange and gel permeation chromatography and phosphate end-group analysis. Gel permeation chromatography showed that between 3.6% and 8.1% of material higher than the hexamer was formed in 3-, 15- and 40-day reactions. The material from a large-scale, 3-day reaction mixture was first fractionated by ion exchange chromatography and the highest molecular weight material then further fractionated by gel permeation chromatography. End-group analysis on the fractions obtained by this procedure showed that 0.67% of the total reaction mixture was polymer with an average chainlength of 13.4; a trace (0.15%) of higher polymer was also formed, but there was insufficient to determine its average chainlength. The prebiological relevance of these findings is discussed.
    Type of Medium: Electronic Resource
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    Journal of molecular evolution 3 (1974), S. 141-150 
    ISSN: 1432-1432
    Keywords: Adsorption ; Clay ; Montmorillonite ; Phosphoramidates ; Polymerization ; Prebiotic
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Nucleoside phosphoramidates derived from polyamines containing at least three amine groups are strongly adsorbed by sodium and magnesium montmorillonite clays even from very dilute solutions. Heating the dried clay-phosphoramidate mixture results in the production of small amounts of the dinucleotides.
    Type of Medium: Electronic Resource
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    Journal of molecular evolution 3 (1974), S. 57-61 
    ISSN: 1432-1432
    Keywords: Aspartic Acid ; Kaolinite ; Optical Activity ; Polymerization ; Adsorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary We have been unable to confirm the recent report that kaolinite catalyzes the polymerization of aqueousd- andl-aspartic acid at different rates. In experiments wheredl-Asp was used, no induced optical rotation was found in the reaction solution. No evidence for polymer (or other product) formation was found whenl-Asp-2-14C was used, and products were searched by paper chromatography and X-ray film autoradiography. Asp is adsorbed by kaolinite, but no selectivity for one or the other enantiomer was observed.
    Type of Medium: Electronic Resource
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Journal of molecular evolution 3 (1974), S. 323-330 
    ISSN: 1432-1432
    Keywords: Prebiotic ; Polymerization ; Deoxythymidine-Oligonucleotides ; Deoxythymidine-Triphosphate ; Cyanamide ; 4-Amino-5-Imidazolecarboxamide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Deoxythymidine 5′-triphosphate in the presence of deoxythmidine 5′-phosphate, cyanamide and 4-amino-5-imidazole carboxamide polymerizes under drying conditions at moderate temperatures (60–90 °C) to yield oligonucleotides of up to four units in length. Enzymatic analysis indicated the majority of these oligomers contained natural 3′–5′ phosphodiester bonds. This reaction offers a possible method for the formation of deoxyoligonucleotides under primitive earth conditions.
    Type of Medium: Electronic Resource
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  • 14
    Electronic Resource
    Electronic Resource
    Springer
    European biophysics journal 1 (1974), S. 55-64 
    ISSN: 1432-1017
    Keywords: Calorimetry ; Circular Dichroism ; Flagellin ; Polymerization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Physics
    Notes: Abstract The heat effects accompanying the isothermalin vitro polymerization ofPr. mirabilis flagellin on short flagella fragments (seeds) have been measured in phosphate buffer pH 7, at various temperatures employing a batch microcalorimeter. Additionally, at 20
    Type of Medium: Electronic Resource
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  • 15
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 13 (1974), S. 781-789 
    ISSN: 0570-0833
    Keywords: Kinetics ; Radical polymerization ; Polymerization ; Reaction mechanisms ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Low molecular reactions are frequently accompanied by side reactions producing a whole spectrum of by-products whose removal in purification operations generally causes little difficulty because the major and side products usually differ sufficiently in their properties. Hence detailed kinetic studies in low molecular chemistry can claim industrial interest only insofar as they aim to reduce the rate of formation of side products. The situation is completely different in polymer chemistry, where the terms major and side product no longer apply. Instead, one obtains mixtures of similar and/or isomeric molecules which differ so little with regard to molecular weight and structure that resolution into pure substances or isolation of pure substances becomes practically impossible. However, since all partial reactions exert a direct influence on the product spread, i.e. the composition and properties of a product mixture are modified by any change in operating conditions, detailed kinetic analyses embracing all relevant partial reactions are an essential prerequisite for the production of defined polymeric products on any scale. This progress report illustrates the importance of kinetics for radical polymerization with the aid of selected examples.
    Additional Material: 4 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    Springer
    Journal of molecular evolution 2 (1973), S. 303-316 
    ISSN: 1432-1432
    Keywords: Polymerization ; Phosphorylation ; Adenosine Cyclic 2′,3′-phosphate ; Oligonucleotides ; Amines ; 2-Aminoethanol ; Amino Acids ; Prebiotic
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary When adenosine cyclic 2′,3′-phosphate is evaporated from solution in the presence of simple catalysts such as aliphatic diamines at alkaline pH, and maintained in a dry state at moderate temperatures (25-85°C), self-polymerization to give oligonucleotides of chainlength up to at least 6 is observed. The products contain an excess of [3′→5′]-linkages over [2′→5′]-linkages. The effects of different catalysts and reaction conditions on the efficiency of the reaction are described. The prebiological relevance of these reactions is discussed.
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  • 17
    ISSN: 0570-0833
    Keywords: Addition polymerization ; Polymerization ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerizability of compounds such as 1,l-disubstituted ethylenes, aldehydes, ketones, isocyanates, and five- and six-membered ring compounds is determined largely by thermodynamic considerations. The transition from non-polymerizability to polymerizability, correspondlng to a change in the sign of ΔG, is often quite sharp. Factors which generally make the free energy of polymerization more negative, and which therefore favor polymerization, are low temperature, high pressure, and high monomer concentration. Additional driving force is sometimes available if the monomer is in the supercooled (glassy) state rather than the crystalline state, or if the polymer crystallizes on formation. Alkyl substituents have an unfavorable effect on polymerizability; halogen substituents have a favorable effect. Many monomers which do not homopolymerize for thermodynamic reasons will copolymerize with a second monomer to the extent of forming copolymers containing 50 or even 66 mol per cent of the first monomer.
    Additional Material: 4 Ill.
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  • 18
    Electronic Resource
    Electronic Resource
    Springer
    Journal of molecular evolution 2 (1972), S. 1-9 
    ISSN: 1432-1432
    Keywords: Polymerization ; Amino Acids ; Primitive Earth ; Chemical Evolution ; Prebiotic Condensation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Chemical evolution on the primitive earth must have involved the condensation ofα-amino acids to peptides under a variety of conditions. Subjecting a mixture of methane, ammonia, and water to an electric discharge in the presence of free amino acids yields small peptides. The dehydration-condensation may have taken place via ammonium cyanide, the hydrogen cyanide tetramer, or aminonitriles. The experiments may be considered genuinely prebiotic and significant in the context of chemical evolution.
    Type of Medium: Electronic Resource
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  • 19
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 11 (1972), S. 974-978 
    ISSN: 0570-0833
    Keywords: Photopolymerization ; Polymerization ; Ketones ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The present article deals with the primary photochemical reactions of carbonyl compounds commonly used as photoinitiators. It is shown that radical formation results mainly from three processes, i.e. hydrogen abstraction, β-cleavage, and α-cleavage. The difference in the suitability of the radicals for chain initiation is discussed.
    Additional Material: 1 Ill.
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  • 20
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 10 (1971), S. 776-786 
    ISSN: 0570-0833
    Keywords: Polymerization ; Polyethylene ; Vanadium ; Chromium ; Catalysis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the present progress report literature data concerning homogeneous catalyst systems based on vanadium and chromium are reviewed and complemented by a combined study of the magnetic properties and the polymerization activity of such systems. The results show that vanadium forms active species as V (III) and as V (II), but chromium only as Cr (II); models are suggested for the polymerization process.  -  A comparison with heterogeneous systems (Phillips catalyst) allows the establishment of some general principles concerning the activity of the catalyst and the properties of the polymers.
    Additional Material: 10 Ill.
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  • 21
    ISSN: 0570-0833
    Keywords: Stereospecific polymerization ; Polymerization ; Polycyclopentene ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of cyclo-olefins, like that of olefins with an internal double bond, is sterically hindered. Within recent years it has become possible to prepare copolymers of these compounds with ethylene, with the aid of anionic coordination Ziegler catalysts. This copolymerization always results in cis-opening of the double bond. Despite the steric hindrance, cyclobutene and cyclopropene have also been homopolymerized, with opening of the double bond. - Rather surprisingly, the best catalysts for homopolymerization of cyclopentene are those which exhibit low activity in the polymerization of ethylene. Ring cleavage occurs with MoCl5/Al(C2H5)3 to give the cis-polypentenamer, whereas WCl6/Al(C2H5)3 gives the trans-polypentenamer. Both polypentenamers exhibit elastomeric properties. - Evidence from infrared spectra and oxidative degradation indicates that the monomer units in the trans-polypentenamer are linked head-to-tail. It is presumably the single bond adjacent to the double bond that is broken. Using X-ray methods at -50 °C, it was possible to determine the crystal structure of the crystalline trans-polypentenamer at about 400% elongation.
    Additional Material: 6 Ill.
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  • 22
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 2 (1963), S. 32-41 
    ISSN: 0570-0833
    Keywords: Polymerization ; Polyethylene ; Titanium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A two-component organometallic catalyst of composition CH3TiCl3·CH3AlCl2 effects high-speed polymerization of ethylene in the presence of chlorinated hydrocarbons at low temperatures. The catalyst does not undergo any alteration in the process. In contrast to the Ziegler catalysts, the titanium remains quadrivalent. Olefins of low-molecular-weight and with branched structures are produced. It proved possible to isolate the primary products of the polymerization at -50 to -100°C and to elucidate the mode of their formation from a knowledge of their structures. The findings are incompatible with either a cationic or anionic reaction mechanism. A novel type of mechanism is proposed, whereby the catalyst is supposed to have an ionic structure and molecular growth proceeds via π-complex formation of the olefin with the titanium cation. The formation of ethylene/olefin copolymers is also discussed.
    Additional Material: 1 Ill.
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  • 23
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 2 (1963), S. 295-308 
    ISSN: 0570-0833
    Keywords: Emulsion polymerization ; Polymerization ; Polymerization ; Alkenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ionizing radiation induces the polymerization of some vinyl monomers in aqueous emulsion with high radiation yields. With identical emulsion compositions, the kinetics of this reaction and the kinetics of emulsion polymerization induced by water-soluble initiators are very similar. The rate of reaction in emulsion polymerization is about one hundred times greater than in bulk polymerization. The initiation of emulsion polymerization by means of ionizing radiation permits uniform “illumination” of the reacting volume, as well as almost any desired variation in the frequency of initiation during the reaction. The sharp decrease in the overall rate of reaction when initiation is interrupted during emulsion polymerization of styrene induced by γ-rays contradicts the earlier concept of sharply separated reaction zones.
    Additional Material: 11 Ill.
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  • 24
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 2 (1963), S. 704-714 
    ISSN: 0570-0833
    Keywords: Titanium ; Alkenes ; Polymerization ; Titanium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: At low temperatures, ethylene and α-olefins (Δ1-olefins or 1-alkenes) are rapidly converted into oligomrs by the two-component organometallic catalyst CH3TiCl3·CH3AlCl2. To achieve smooth oligomerizations, aromatic or chlorinated hydrocarbons must be used as solvents. Although the activity of the titanium-carbon bond is enhanced by the aluminum component of the catalyst, the aluminum and its methyl group do not participate in the reaction proper; the latter proceeds exclusively at the titanium-carbon bond. The reaction will olefins can be used as an analytical method for the quantitative determination of the titanium-carbon bond in admixture with the organoaluminum component. It is thus possible to follow the reaction leading to formation of the catalyst from titanium tertrachloride, as well as the processes occurring at the titanium-carbon bond during the oligomerization of olefins. All the observations indicate that the catalyst possesses an ionic structure which is determined by the solvent. It is shown that the initial reaction step probably involves formation of a complex between the olefin and the alkyltitanium cation. The reaction scheme proposed is based on organometallic reactions which are characterized by carbanion and hydride transfers within the olefin-cation complex. This mechanism, which is unusual for Ziegler catalysts, is due to the predominance of hydride transfers.
    Additional Material: 2 Ill.
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  • 25
    ISSN: 0570-0833
    Keywords: Pyrrolidone ; Polyamides ; Fibers ; Lactams ; Polymerization ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The industrial production of capryllactam (1-azacyclononan-2-one) and of laurolactam (1-azacyclotridecan-2-one) starts with cyclization of acetylene or butadeine to give cyclooctatetraene or cyclooctadiene, or cyclization of butadiene to give cyclododecatriene. Further steps are: oxidation of the cyclic hydrocarbon to the ketone, formation of the oxime, and rearrangement of the latter with sulfuric acid. Pyrrolidone can be prepared from acetylene and formaldehyde by way of butyrolactone. The behavior of the lactams during polycondensation is described and the properties of the resulting fibers are compared with those of the known polyamide fibers.
    Additional Material: 2 Ill.
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  • 26
    ISSN: 0570-0833
    Keywords: Lactams ; Polymerization ; Fibers ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: β-Lactams can be prepared by cyclization of β-aimno acid esters. Recently they have become available also from olefins by addition of N-carbonysulfamyl chloride (isocyanatosulfonyl chloride) and from aldehydes by reaction with N-carbonylsulfamyl chloride and ketene. Condensative or anionic polymerization results in polyamides the chains of which contain many more amide groups than the chains of polyamides of the nylon-6 type. Hence the new polymers resemble silk moreclosely. Fibers and films can be prepared from solution.
    Additional Material: 7 Ill.
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