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  • 2000-2004  (5)
  • 1980-1984  (12)
  • 1960-1964  (6)
  • 1920-1924
  • 1905-1909
  • 1880-1889
  • 1800-1809
  • Polymerization
  • 1
    ISSN: 1436-3771
    Keywords: Key words Composite resins ; Polymerization ; Marginal adaptation ; Light intensity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  The aim of this study was to evaluate the effect of a rapid photopolymerization method on the marginal integrity of composite fillings. Ninety two-surface cavities were prepared in extracted human molars using the SonicSys preparation system. All cavities were bonded with one bonding agent (Syntac) and filled with a microfilled composite (Herculite XRV), a heavy filled composite (Z100 MP), and an Ormocer (Definite) in two increments. Each increment had a thickness of approximately 1.5 mm and was polymerized using either halogen light or the plasma light of Apollo 95 E. In this process, six trial groups each containing 15 fillings were created. After replicas were made, the test teeth were subjected to a thermocycling process of 2000 temperature cycles (5°C/55°C) followed by a wear simulation of 50,000 stress cycles each with 50 N. This was followed by the creation of a second set of replicas, quantitative margin analysis, and dye penetration. A significant (P〈0.05) influence of the thermomechanical stress and a significant (P〈0.05) influence of the factor ”material” were shown for the margin criterion ”continuous margin” using MANOVA. The factor ”light source” produced no significant influence (P=0.57) on the amount of continuous margin. During the dye penetration, no significant differences between the polymerization methods could be established with the materials Herculite XRV and Z100 MP (H-test according to Kruskall and Wallis). Only with the material Definite was a significantly higher dye penetration observed at the occlusal measuring point in the plasma light group. A rapid polymerization with high light intensity had no adverse effects on the margin quality within the limitations of this in vitro study. However the marginal integrity might have been influenced by the chosen adhesive system/composite resin combination, which does not represent the respective product line. Additionally, further studies ought to show which exposure time is necessary for a sufficient degree of conversion.
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  • 2
    ISSN: 1572-8935
    Keywords: Functional monomers ; Polymerization ; Copolymerization ; Kinetic studies ; Reactivity ratios
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract 1-Cyanoethanoyl-4-acryloylthiosemicarbazide (CEATS) was synthesized for the first time as a new chelating monomer. Its structure was confirmed by both elemental and spectral analyses. Radical polymerization and copolymerization of CEATS was been carried out in dimethylformamide (DMF) in the presence of azobisisobutyronitrile (AIBN) as an initiator. Kinetic studies for the polymerization behavior of CEATS were performed. The complex formation of the CEATS monomer and polymer (PCEATS) with Cu II cation was investigated and its stability constant determined. The rate of copolymerization of CEATS with some conventional monomers, namely vinyl acetate, methyl methacrylate and acrylonitrile, was measured as a function of the mole fraction of the monomers. The reactivity ratios (r1, r2) for the various copolymer systems investigated together with the Q and e values of the CEATS monomer were determined. Moreover, the thermal gravimetric analysis of the prepared polymers and their copolymers with acrylonitrile were also studied.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Journal of wood science 46 (2000), S. 143-148 
    ISSN: 1611-4663
    Keywords: α-Pinene ; Phenol ; Formaldehyde ; Polymerization ; Condensation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Synthesis conditions of terpene-phenol-aldehyde resin with a high softening point were studied based on the reactions amongα-pinene, phenol, and formaldehyde. A suitable catalyst system and the best processing conditions were obtained by laboratory experiments. The influence of the raw materials ratios, reaction temperature, reaction time, and catalyst dose on the softening point, yield, and color of the synthesized resin was examined. The physical and chemical characteristics of the resin were determined: softening point ≥140°C (ball and ring method); color value ≤7 (Gardner); acid value (KOH mg/g) 〈1; bromine value (Br2 mg/100g) 〈64; saponification value (KOH mg/g) 〈1; average molecular weight ∼830. The yield of resin was more than 85% (based on the total raw material).
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 278 (2000), S. 150-154 
    ISSN: 1435-1536
    Keywords: Key words Hydrolysis kinetics ; Polymerization ; Microemulsions ; Aspirin ; Styrene
    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 Two kinds of chemical reactions were studied in two different microemulsion systems: cetyltrimethylammonium bromide/1-butanol/10 and 25% n-octane/water and sodium dodecyl sulfonate/1-butanol/20% styrene/water. One reaction is a hydrolysis reaction, in which aspirin and 2,4-dinitrochlorobenzene were used as the hydrolysis substrates. The second reaction is the polymerization of styrene, which was initiated by using two initiators, water-soluble K2S2O8 and oil-soluble 2,2′-azobis(isobutyronitrile), and, at the same time, the polymerization of acrylamide, which was initiated by NaHSO3, was also studied. All the hydrolysis reaction experimental results show that the hydrolysis is greatly affected by the structures and the structural transitions of microemulsions. The hydrolysis rates are higher in water-in-oil (W/O) microemulsion media and decrease with the addition of water. The rates increase in bicontinuous (BC) microemulsions and decrease in oil-in-water (O/W) microemulsions. The transition points of the hydrolysis rates occurred at the two microemulsion structural transition points from W/O to BC and from BC to O/W. The polymerization relationships between the conversions of styrene, the molecular weights of polystyrene and the water contents of the microemulsion system were obtained. The effects of microemulsion structures on the sizes of the polystyrene particles and on the molecular weights of the polymers are discussed. Polystyrene particles with diameters of 10–60 nm were observed by microscopy. Our experimental polymerization results show that microemulsions are suitable as media for the production of polymers, the molecular weights and the particle sizes of which can be controlled and predicted by variations in microemulsion structures.
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  • 5
    ISSN: 1434-1948
    Keywords: Aluminum ; Alkoxides ; Lactone ; Ring-opening ; Polymerization ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of trialkylaluminum Al2R6 (R = Me, Et) with 2,2′-methylenebis(6-tert-butyl-4-methylphenol) (mbmpH2) gives the dimeric mono(alkyl) complex [Al(mbmp)R]2 with bridging oxygen atoms. Reaction of [Al(mbmp)R]2 with one equiv. of 2-propanol results in the formation of the dimeric isopropoxide [Al(mbmp)(μ-OiPr)]2. Single-crystal X-ray analysis shows a C2h-symmetric structure with a planar Al2O2 core. Monomeric methylbis(2,6-di-tert-butyl-4-methylphenolato)aluminum, AlMe(OC6H2-2,6-tBu2-4-Me)2 (MAD), was found to react with one equiv. of 2-propanol to give a dimeric isopropoxide [AlMe(OC6H2-2,6-tBu2-4-Me)(μ-OiPr)]2 in which the bulky phenolate, instead of the methyl group, has been displaced. According to the single-crystal X-ray structure analysis, the molecule contains a similar Al2O2 core, but the two 2,6-di-tert-butyl-4-methylphenolato ligands are cis- and orthogonally arranged to each other. ε-Caprolactone is polymerized at 50 °C in toluene in a controlled manner by [Al(mbmp)(μ-OiPr)]2, to give poly(ε-caprolactone) with high molecular weights and narrow molecular weight distributions (Mw/Mn 〈 1.50). The low efficiency values (number of polymer chains initiated per aluminum atom) imply that [Al(mbmp)(μ-OiPr)]2 exists in a monomer-dimer equilibrium. The polymerization of ε-caprolactone by [AlMe(OC6H2-2,6-tBu2-4-Me)(μ-OiPr)]2 is faster, but somewhat less controlled.
    Additional Material: 2 Ill.
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  • 6
    ISSN: 1432-1432
    Keywords: Evolution ; Gene family ; Balbiani ring genes ; Repetitive sequences ; Structural proteins ; Protein conformation ; Polymerization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary The large, repetitive Balbiani ring (BR) genes, BR 1, 2, and 6, inChironomus tentans originated from a short ancestral sequence and have all evolved according to analogous amplification schemes. We analyzed the structures of the BR-encoded secretory proteins and defined the parts that have been conserved during the evolutionary process. The BR products show striking similarities, with the BR 1 and BR 2 products being more similar to each other than to the BR 6 product. In the constant (C) region of the repeat units, 7 of the 30 amino acid residues are strictly conserved; 4 of these are the cysteine residues. The subrepeat (SR) regions of all the BR products are dominated by repeated tripeptide elements rich in proline and charged amino acid residues. Most of the amino acid replacements in both regions are conservative. Secondary structure predictions suggested that the C regions of the BR 1 and BR2 products have several elements of secondary structure: an α-helix, a β-strand, and one or two reverse turns, as in “globular structures.” The prediction for the C region of the BR 6 product is similar but lacks a β-strand. The predictions for the intervening SR regions appear less conclusive, but are clearly different from those for the C regions, and suggest regular structures not differing in their conformational elements. The SR regions evolved from an ancestor sequence similar to the C region; thus, the BR products seem to represent an example of evolution from one structure to two differently folded products. It is proposed that the alignment and polymerization of the long BR proteins could be promoted by the repetitive structure of the molecules, due to the possibility of forming disulfide bridges between half-cystine residues and electrostatic interactions between the charged residues of the SR regions. The divergence among the BR products is discussed in relation to possible functional differences among the members of the BR gene family.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 261 (1983), S. 40-44 
    ISSN: 1435-1536
    Keywords: Polymerization ; Acrylamide ; Methacrylamide ; Peroxydiphosphate
    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 The kinetics of aqueous polymerization of acrylamide and methacrylamide initiated by potassium peroxydiphosphate has been investigated. The kinetic orders with respect to peroxydiphosphate and monomer were close to 0.5 and 1 respectively. Overall activation energies were computed and a suitable kinetic scheme suggested. Comparison with kinetic studies of the analogous acrylamide polymerization by peroxydisulphate shed doubt on the cage effect interpretation of the complex order with respect to monomer.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 261 (1983), S. 188-189 
    ISSN: 1435-1536
    Keywords: Polymerization ; kinetics ; redox polymerization ; acrylamide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Journal of statistical physics 31 (1983), S. 363-378 
    ISSN: 1572-9613
    Keywords: Polymerization ; coagulation equation ; RA f model ; A gRBf−g model ; random polycondensation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract This paper gives the equilibrium distribution of polymer sizes for Flory'sA g RB f−g model of polymerization. In this model, the polymers are composed of structural units withg functional groups of the typeA and (f-g) functional groups of the typeB. Reaction is subject to three conditions: (1) Functional groups of the typeA react only with those of typeB, and vice versa. (2) Intramolecular reactions do not occur [and therefore only branched-chain (noncyclic) polymers and formed]. (3) Subject to conditions (1) and (2), all functional groups are equally reactive. The derivation employs Stockmayer's statistical mechanical method (first used on Flory'sRA f model), coupled with a recursion giving the number of distinct polymers which may be assembled fromk units of theA g RB f−g type. We also give distributions for a limiting case of theA g RB f−g model, the so-calledA g RB ∞ model. This paper completes the solution of the Smoluchowski coagulation equation (monodisperse case) for the kernelsa ij =A + B(i +j)+ Cij. The proof will be given in another publication.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 22 (1983), S. 440-455 
    ISSN: 0570-0833
    Keywords: Initiation ; Addition ; Polymerization ; Alkenes ; C-C coupling ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Spontaneous addition and polymerization reactions of alkenes of different electron-densities result in a wide variety of small organic molecules and high polymers. Tetramethylenes are proposed as key intermediates, i.e. resonance hybrids of 1,4-diradical and zwitterionic limiting structures. Their character is determined by the substituents at the terminals: Zwitterionic character is favored by strong donors, such as alkoxy and dialkylamino groups, at the carbenium center and strong acceptor group such as diesters and cyano-esters, at the acceptor end, and aryl and vinyl groups as donors. Zwitterionic tetramethylenes initiate ionic homopolymerization, while diradical tetramethylenes initiate alternating copolymerization, thus providing an extremely sensitive technique for the detection and characterization of these intermediates. The effects of the donor and acceptor substituents can be arranged as an “Organic Chemist's Periodic Table”, wherein the areas of mechanistic change clearly emerge and which provides predictive capability. - This unifying concept of bondforming initiation is extended to spontaneous addition and polymerization reactions of heteroatom acceptor molecules and 7,7,8,8-tetrasubstituted quinodimethanes and of compounds possessing labile σ-bonds, such as halogens and peroxides. Radical-ion pairs, charge-transfer complexes and adventitious impurities are excluded as significant initiators.
    Additional Material: 1 Ill.
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    Archives of microbiology 132 (1982), S. 14-21 
    ISSN: 1432-072X
    Keywords: Kraft lignin ; Phanerochaete chrysosporium ; Inocula ; Biodegradation ; Polymerization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Bioalteration of the organic-soluble ether-insoluble fraction of Kraft pine lignin (KL-O) was studied. Various types of inocula ofPhanerochaeta chrysosporium were compared using a standing mode of cultivation under nitrogen limitation. Pellet inoculated and mycelial cultures required a period of about 10 days to become ligninolytically active. When spores were used as inoculum the bioalteration of lignin commenced earlier but the rate was considerably less. The total decrease in absorbance measured amounted to 61% within 20 days after addition of lignin to active mycelial cultures. This corresponded to a reduction of 50% in Klason lignin. Further reduction was possible only when the free lignin was extracted from the culture, purified and mixed with new active cells. Elemental analysis, Klason lignin content, absorptivity coefficient, molecular weight distribution and the presence of saccharides and proteins for free and “cell recovered” lignin were compared with KL-O. Microscopic observation showed the formation of new out-growths in the form of short hyphae appearing concurrently with ligninolytic activity.
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 260 (1982), S. 771-775 
    ISSN: 1435-1536
    Keywords: Polymerization ; Acrylonitrile ; Methylmethacrylate ; Peroxydiphosphate-Thioglycollic acid
    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 The kinetics of the aqueous polymerization of acrylonitrile and methyl methacrylate initiated by the peroxydiphosphate-thioglycollic acid redox system was investigated at 40, 45, 50, 55, and 60 °C. The rates of polymerization were measured at different concentrations of oxidant, activator and monomer. From the results, it was concluded that the polymerization reaction is initiated by an organic free radical arising from the peroxydiphosphate-thioglycollic acid system and termination by mutual type. On the basis of experimental observations of the dependence of the rate of polymerization,R p on various variables, a suitable kinetic scheme has been proposed.
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Monatshefte für Chemie 112 (1981), S. 287-292 
    ISSN: 1434-4475
    Keywords: Activation energy ; Kinetics ; Methyl-vinyl ketone ; Polarography ; Polymerization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The homogeneous polymerization of methyl-vinyl ketone in diluted methanol solutions in presence of proton donors is studied using the polarographic method. The effect of the cation of the indifferent electrolyte is investigated as well as the influence of small quantities of H2O. Suggestions were made about the possible mechanisms of these influences in the general scheme of the process proposed byHolleck et al.
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  • 14
    Electronic Resource
    Electronic Resource
    Springer
    European biophysics journal 7 (1981), S. 195-203 
    ISSN: 1432-1017
    Keywords: Association ; High pressure ; Hydrophobic interactions ; Polymerization ; Tobacco mosaic virus protein
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Physics
    Notes: Abstract Tobacco mosaic virus protein in phosphate buffer pH 6.5–7.0 (I=0.1 M) shows endothermic polymerization accompanied by water release of the capsomers. At protein concentrations c ∼ 2 mg/ml the transition temperature is T *=20 ± 1
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  • 15
    Electronic Resource
    Electronic Resource
    Springer
    Archives of microbiology 125 (1980), S. 233-237 
    ISSN: 1432-072X
    Keywords: Laccase ; Thioglycolic acid ; Lignin degradation ; Polymerization ; Coniferyl alcohol ; Catechol ; Fomes annosus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract 1. Thioglycolic acid, a Cu-chelating agent, totally inhibited extracellular laccase activity without affecting growth and morphology of Fomes annosus. 2. In the presence of thioglycolic acid Fomes annosus cleaved high molecular weight lignosulfonate with a molecular weight range of 2×106 to 1000. In the absence of thioglycolic acid the polymerizing activity of laccase prevented the detection of lignosulfonate breakdown products. 3. Oxidative polymerization of a lignin monomer, coniferyl alcohol, occurred in the presence but not in the absence of laccase activity. 4. Catechol and guaiacol added to the medium at a concentration of 2 mmol, are normally oxidized by fungal laccase and strongly inhibit growth. Presence of thioglycolic acid prevented the oxidation of these phenols and simultaneously permitted normal growth.
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  • 16
    ISSN: 0018-019X
    Keywords: Enzymatic Peptide Synthesis ; Papain ; Methionine ; Polymerization ; α-Amino Acid Ester ; Peptides ; Sulfoxide ; Sulfone ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Water-insoluble oligomers were synthesized from L-methionine ethyl ester with papain as the catalyst. L-Oligomethionine was obtained in yields of 50% when synthesis was carried out in highly concentrated citrate buffer at pH 5.5. Yields of up to 85% were obtained when the enzymatic synthesis proceeded in distilled water at pH 6.5, the pH being strictly maintained. The insoluble polymer was converted to highly water-soluble sulfoxide and sulfone derivatives, which consist mainly of an octamer with low amounts of heptamer or hexamer. Most of the carboxyl terminals still contained the ethyl ester group, only a minor part being present in the free acid form. The potential of the enzymatic approach for the synthesis of optically pure and monodisperse oligomers of α-amino acids is discussed.
    Additional Material: 4 Ill.
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  • 17
    ISSN: 0570-0833
    Keywords: Stereospecific polymerization ; Polymerization ; Propylene ; History of chemistry ; Tacticity ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In 1955 Natta and his co-workers from the Istituto di Chimica Industriale del Politecnico di Milano reported the properties of highly crystalline polypropylene and other poly-α-olefins[1] which posses, at least in long sections of the main chain, asymmetric carbon atoms of the same absolute configuration (isotactic poly-α-olefins). The discovery of the new crystalline polymers was judged at that time “revolutionary in its significance”[2] and heralded a new era in polymer science and technology. Indeed, crystalline polypropylene, because of its relatively high melting point and its outstanding mechanical properties, has found very extensive application in the field of plastics films and fibers. - 25 years after this publication, it is worthwhile examining the further developments following this discovery which has had such a great scientific and industrial impact, and the problems which are still open concerning the structure of the catalytic centers and the mechanisms by which practically completely stereoregular polypropylenes are formed.
    Additional Material: 6 Ill.
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  • 18
    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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  • 19
    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.
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  • 20
    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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  • 21
    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.
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  • 22
    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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  • 23
    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.
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