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  • Articles  (25,695)
  • Springer  (25,695)
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  • Chemistry and Pharmacology  (25,695)
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  • Articles  (25,695)
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  • 1995-1999
  • 1990-1994  (11,576)
  • 1965-1969  (14,119)
  • 1955-1959
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  • 1
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    Springer
    Polymer bulletin 28 (1992), S. 33-40 
    ISSN: 1436-2449
    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: Summary Substituted poly(cyclohexene)s, used as poly(phenylene) precursors, have been prepared by radical polymerization of cyclohexadiene-1,2-diol derivatives containing various leaving groups. The precursors were converted into poly(phenylene) either by curing at elevated temperatures or by deep-UV exposure in the presence of a photoacid generator. These reactions were investigated by both IR and UV analysis. Our results with the conversion of precursors into poly(phenylene) via photoaromatization suggest that polyphenylene precursors can be imaged by deep-UV microlithography (as a new class of photoimageable thermally stable polymers).
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  • 2
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    Polymer bulletin 28 (1992), S. 117-122 
    ISSN: 1436-2449
    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: Summary The cationic polymerization of various α- and β-substituted vinyl ethers, initiated by 1-iodo-1-(2-methylpropyloxy)ethane 1 and tetrabuty lammonium perchlorate (TBAP) was investigated. The polymerization of 2,3-dihydrofuran (DHF, 3a) in CH2Cl2 at -40°C proceeds via opening of the ethylenic double bond and yields polymers with narrow molar mass distributions and high glass transitions. The number average of molar mass increased linearly with conversion. Under these conditions, a controlled polymerization of two propenyl ethers (1-ethoxypropene 2a and 2-methoxypropene 2b) and two other cyclic unsaturated ethers (3,4-dihydro-2H-pyran 3b and 5-methyl-2,3-dihydrofuran 3c) could not be achieved. Either transfer reactions or the decomposition of 1 prevented the formation of high molar mass polymers of these vinyl ethers.
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  • 3
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    Polymer bulletin 28 (1992), S. 555-560 
    ISSN: 1436-2449
    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: Summary 3-Vinylbenzothiophene was synthesized and its copolymerization with methyl methacrylate and n-butyl acrylate was investigated. The copolymerizations were performed according to an experimental design scheme and the results were analyzed using a nonlinear error-in-variables method. The 3-vinylbenzothiophene was found to be a reactive monomer with reactivity ratio values similar to those of 2-vinyl thiophene.
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  • 4
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    Polymer bulletin 28 (1992), S. 561-568 
    ISSN: 1436-2449
    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: Summary Isotactic (it-) and syndiotactic (st-) MMA oligomers from 19-mer to 29-mer could be isolated efficiently from it-PMMA ( $$\overline {DP}$$ = 28.6) and st-PMMA ( $$\overline {DP}$$ = 28.6) (sample load: 50 mg) by the SFC using a 10 mm i. d. x 250 mm column packed with silica gel. DP of each isolated oligomer was determined by FD mass spectroscopy, and the values agreed well with those calculated from the relative intensity of 1H NMR signals due to CH3O- and the terminal t-C4H9-groups. Glass transition temperature (T g) of the it-28-mer measured by DSC was 34.5°C, which was higher than that of the it-PMMA by 6.5°C. T g of both the it-and st-oligomers increased linearly with DP in the range of DP=20∼29. A 1: 1 mixture of the it- and st-27-mers annealed at 140°C showed an endothermic transition at 102.3°C which was attributable to melting of stereocomplex, whereas an annealed 1: 1 mixture of the it- and st-PMMAs had a much broader endotherm around 80∼140°C.
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  • 5
    ISSN: 1436-2449
    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: Summary The coordination structures of Cu(II) complexes of amino functions supported on polyacrylamides with varying extents of NNMBA-crosslinks were followed by EPR techniques. The geometry of the Cu(II) complexes changes with increasing crosslinking. The covalency of the Cu-N bond also depends on the extent of the NNMBA-crosslinking in the polymer-support.
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  • 6
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    Polymer bulletin 28 (1992), S. 601-606 
    ISSN: 1436-2449
    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: Summary The sorption behaviour of copper (II) and uranium (VI) ions on branched poly(ethylenimine) (BPEI) bridged with bifunctional crosslinkers (CR), 1-chloro-2,3-epoxypropane, 1,3-dibromopropane and 1,2-dibromoethane with various degress of crosslinks has been examined. The effect of crosslinking on the extent of sorption and thermal stability is reported.
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  • 7
    ISSN: 1436-2449
    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: Summary The mesophase formation was observed from the system of mixed organic polymer (hydroxypropyl cellulose) and inorganic polymer (imogolite) in acetic acid aqueous solution. The phase diagram of the mesophase formation was drawn as a function of imogolite content. The mesophase structure was found to change from the helicoidall arrangement of nematic sheets to the pile of pleated nematic sheets with increasing imogolite content.
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  • 8
    ISSN: 1436-2449
    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: Summary First unsaturated polyester fibers were prepared starting from stereoregular, macromolecular poly(octamethylene fumarate). Fibers obtained from octamethylene copolyesters of fumaric and terephthalic acids manifested improved mechanical properties and higher melting points. All unsaturated polyester fibers prepared in the study, based on the homopolymer and on copolymers of fumaric acid, even those containing as low as 10% of fumaric acid residues, are able to be covalently bonded to an unsaturated polyester matrix.
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  • 9
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    Polymer bulletin 28 (1992), S. 633-638 
    ISSN: 1436-2449
    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: Summary Propylene oligomers containing isopropenyl end group have been prepared by thermolysis of atactic polypropylene. The chain-end structures and the number-avarage isopropenyl chain end functionality was determined in the product by C-13 NMR spectroscopy. Molecular weight of the oligomers were between 300 and 1000, as characterized by GPC. Conditions leading to the formation of propylene oligomers with number-average isopropenyl chain end functionality of 1.0, have been worked out.
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  • 10
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    Polymer bulletin 28 (1992), S. 653-656 
    ISSN: 1436-2449
    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: Summary The photoaddition of aromatic dithiols (1) onto aliphatic alkenes (2a-2c) yielding polysulfides is studied. Polysulfides having anti-Markownikow and Markownikow moieties in the main chain are obtained by the reaction of dithiols (1) with ethyleneglycoldivinylether (2a). The unusual Markownikow orientation is explained on the basis of a radical cation intermediate.
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  • 11
    ISSN: 1436-2449
    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: Summary Radical polymerizations of vinyl monomers using a initiator of 2,2′-azobis(2-amidinopropane) dihydrochloride on monodispersed silica colloid led to formation of spherical polymer/SiO2 composites, retained particle size. Addition of hydroxypropyl cellulose to the reaction system resulted in yielding excellent dispersible composites into ethanol by short period ultrasonic irradiation. The polymerization of styrene in the presence of mercapto-amine or carboxylic acid derivatives could successfully introduce amino or carboxyl group on the Poly(styrene)/SiO2 composite.
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  • 12
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    Polymer bulletin 28 (1992), S. 689-695 
    ISSN: 1436-2449
    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: Summary The interrelation between the electrical conductance, σ and some chemically modified cellulose molecule produced through partial substitution of the hydroxyl groups by different groups namely, acetate, methoxyl, carboxymethyl and sodium carboxymethyl has been studied in the temperature ranges 283–333 k. The results show that σ of the examined samples change in the descending order: sodium carboxymethyl cellulose 〉carboxymethyl cellulose 〉methyl cellulose〉cotton cellulose〉cellulose acetate. The variable response of σ to the chemical modification and the physical changes of cellulose accompanying such modification has been discussed in terms of the molecular structure, chain flexibility and degree of polymerization of the examined samples.
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  • 13
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    Polymer bulletin 28 (1992), S. 697-702 
    ISSN: 1436-2449
    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: Summary Acidic parameters according to the GUTMANN's acceptor numbers (AN) of cellulose acetates and unmodified cellulose have been determined by means of the negatively solvatochromic probe dye Fe(phen)2(CN)2. Unmodified cellulose possesses a relatively high acceptor strength due to cooperative hydrogen bonds while increasing acetate contents in the polymer chain lower the acceptor strength. The dependence of AN on the acetate content can be used to estimate the degree of substitution (DS). Pecularities in the substitution interval (DS=0 to DS=1.5) are discussed.
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  • 14
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    Polymer bulletin 28 (1992), S. 677-681 
    ISSN: 1436-2449
    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: Summary The complex forming poly[(ethylene glycol-co-proplene glycol)-g-acrylamide]: polyacrylic acid interpenetrating polymer network hydrogel is able to bend under electric field “stimuli”. pH, ionic strength gradients and voltage can influence it's bending degree. So we may improve the sample' “responsive” speed through manipulating those factor in the further study in order to put it into the biomedical application.
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  • 15
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    Polymer bulletin 28 (1992), S. 449-450 
    ISSN: 1436-2449
    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: Summary An original way of reducing composition heterogeneity has been proposed for copolymers obtained at high conversions. The main idea underlying this method consists in application as initiators of special compounds (iniferters) leading to alteration of the mechanism of polymer chain growth.
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  • 16
    ISSN: 1436-2449
    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: Summary A reaction scheme based on propagation and intramolecular chain transfer steps is proposed for the anionic homopolymerization of epoxides initiated by tertiary amines. Chain transfer regenerates a living chain and gives a dead chain with terminal vinilydene unsaturations and hydroxy groups. The possibility of generating phenols or substituted phenols is also considered. Molecular-mass distributions were predicted as a function of conversion by both kinetic and Monte Carlo methods. Predictions were compared with experimental results reported in the literature. The evolution of the number-average degree of polymerization could be reasonably predicted.
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  • 17
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    Polymer bulletin 28 (1992), S. 481-487 
    ISSN: 1436-2449
    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: Summary The coefficient of thermal expansion is measured for irradiated Polyvinyl Chloride (PVC) from 10K to 340K. The samples of PVC are irradiated, up to 500 Mrad in steps of 100 Mrad, in air at room temperature by using Co gamma rays with a dose rate of 0.3 Mrad/h. The PVC is an amorphous sample which is confirmed by X-ray diffraction. The coefficient of thermal expansion is found to decrease with radiation dose from 10K to 110K and it increaseswith radiation dose from 110K to 340K. The results are explained on the basis of radiation induced degradation of the sample.
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  • 18
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    Polymer bulletin 28 (1992), S. A4 
    ISSN: 1436-2449
    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
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  • 19
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    Polymer bulletin 28 (1992), S. 497-503 
    ISSN: 1436-2449
    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: Summary The synthesis of telechelic monodispersed diols produced from the radical telomerization of an excess of undecylenol with commercialy available α, ω-dithiols HSC2H4XC2H4SH (X=0, S or CH2) initiated by peroxides is presented. In each case, the diols were obtained selectively and quantitatively and they were characterized by both 1H and 13C NMR. Their physical characteristics (Tg, Tm and decomposition temperatures) were determined. Such compounds are thermally more stable than polydispersed telechelic commercially available diols.
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  • 20
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    Polymer bulletin 28 (1992), S. 505-509 
    ISSN: 1436-2449
    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: Summary The anionic polymerization of dimethylphenylvinylsilane with sec-butyllithium/N,N,N′,N′-tetramethylethylenediamine (TMEDA) was investigated. The polymerization proceeded up to 100% yield and afforded the polymer having isomerized-structure units. The polymerization was accompanied by chain transfer reaction to the monomer and the polymerization rate in the presence of TMEDA was much lower than in the absence of TMEDA.
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  • 21
    ISSN: 1436-2449
    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: Summary Methacrylation of triglycidyl triphenyl methane (via methacrylic acid) has been done using three catalysts: dimethyl dodecyl amine (DMDA), tetrabutyl ammonium bromide (TBAB) and chromium (III) diisopropyl salicylate (Cr Dips). The reaction has been followed by epoxy colorimetric titration, CPG and 1H NMR. This study has shown the superiority of chromium catalysis because of its rapidity and ease of process. Then, these cured products (TACTIX and methacrylated TACTIX) show homogeneous Tg values which are higher than 200°C.
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  • 22
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    Polymer bulletin 28 (1992), S. 639-644 
    ISSN: 1436-2449
    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: Summary Polyesters from 3,3′-bis(chloromethyl)oxacyclobutane and dipotassium isophthalate were obtained by phase transfer catalysis using different catalysts and solvents. The products were characterised by IR,1H-NMR and DSC.
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  • 23
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    Polymer bulletin 28 (1992), S. 645-652 
    ISSN: 1436-2449
    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: Summary Polycarbonates, polythiocarbonates, and polyesters from 1,1,3-trimethyl-3-(4′-hydroxy-phenyl)-4-indanol were synthesized using phase transfer conditions. THe effects of several catalysts and reactions times were evaluated by the yields and inherent viscosities. Phase transfer catalysis was not an efficient technique due to the rigid structure of the diphenol with the indanic group. The results were compared with that obtained with a diphenol having the same number of carbon atoms but forming an aliphatic side chain.
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  • 24
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    Polymer bulletin 28 (1992), S. 657-662 
    ISSN: 1436-2449
    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: Summary 1,2,3-Triphenylcyclopropene (TPCP) is a powerful retarder for polymerizations of methyl methacrylate (MMA) and styrene initiated by benzoyl peroxide or azobisisobutyronitrile. End-groups in polymers of MMA were studied by 13C-NMR spectroscopy and also, in the case of the peroxide, by using radioactive initiator. It was shown that, towards the benzoyloxy and 1-cyano-1-methylethyl radicals, the reactivity of TPCP exceeds that of MMA by factors of about 60 and three respectively at 60°C. TPCP can be used to introduce into polymers end-groups of special types.
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  • 25
    ISSN: 1436-2449
    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: Summary The influence of solvent on polyvinylpyrrolidone (PVP) and polyitaconic acid monomethylester (PMMI) sterecomplex formation was studied by means of laser light scattering and viscometry. Several phase changes were observed, from homogeneous solution to precipitates and gels. Responsible of this behaviour are hydrogen bonding, Coulombic forces, or hydrophobic interaction in aqueous medium.
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  • 26
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    Polymer bulletin 28 (1992), S. 703-707 
    ISSN: 1436-2449
    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: Summary The Lewis and Mayo's rule, used so far for the determination of r1 and r2, is presently applied for the simultaneous determination of partial monomers conversions α1 and α2; whereas the integration of the Skeist's rule gave global conversion α only. An experimental verification is performed for the cotelomerization of MMA and maleic anhydride with dodecyl mercaptan as telogen, and it gives a very good correlation.
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  • 27
    ISSN: 1436-2449
    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 An anomalous effect on the twisted intramolecular charge transfer (TICT) phenomenon of 4-(N,N-dimethylamino) benzonitrile (DMABN) dissolved in elastomers such as poly(propylene oxide), poly(ethylene oxide) has been observed. Under irradiation, the normal fluorescence of DMABN in these matrices has been found to increase strongly while the emission arising from the TICT state decreases slightly.
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  • 28
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    Polymer bulletin 29 (1992), S. 661-668 
    ISSN: 1436-2449
    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: Summary In this paper, the polymerisation of a conjugated liquid crystalline diacetylene is reported. The structure of the polymer is discussed in relation to results from spectroscopic studies and molecular weight determinations. The polymer has a backbone structure analogous to that of other polydiacetylenes.
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  • 29
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    Polymer bulletin 29 (1992), S. 675-679 
    ISSN: 1436-2449
    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: Summary The preparation of a novel family of “liquid-crystalline” polyamide network gels is described. In these networks, the segments are stiff and longer than the critical axial ratio for mesomorphic behavior. The junctions are trifunctional and flexible. The gels are intensely birefringent in the relaxed nascent state, unlike fully rigid or fully flexible gels. The birefringence of the present gels is clearly associated with the coexistence in them of both long, stiff mesogenic segments and flexible trifurcated junctions. Thermal studies of the gels indicate very strong attractive interactions between the networks and the solvent.
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  • 30
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    Polymer bulletin 29 (1992), S. 697-704 
    ISSN: 1436-2449
    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 Novel poly(acenaphtylene-b-isobutylene-b-acenaphtylene) (PAc-PIB-PAc) triblock copolymers exhibiting thermoplastic elastomer (TPE) properties have been prepared. The synthesis involved the addition of acenaphtylene (Ac) to living polyisobutylene dications (⊕PIB⊕) obtained by living isobutylene (IB) polymerization induced by the dicumyl methyl ether (DiCumOMe)/TiCl4 initiating system at-80°C. The triblocks contain very short polyacenaphtylene (PAc) blocks (Mn≈9,000) and consequently yield very soft, low modulus TPEs. Efforts to develop conditions for the living carbocationic polymerization (LC⊕Pzn) of Ac have failed.
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  • 31
    ISSN: 1436-2449
    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: Summary The cyanoethylation of cyclopentadiene was examined under a variety of reaction conditions. Approximately 9% of cyclopentadiene was converted to the desired hexa(β-cyanoethyl)cyclopentadiene when the amount of acrylonitrile to cyclopentadiene was increased from 2 to 7 equivalents under phase transfer conditions. The low conversion is due to competitive formation of various unreactive side-products. For example, termination leading to less-highly substituted products was confirmed by isolation of crystalline 1,1,2,3,4-penta(β-cyanoethyl)cyclopentadiene. Another side product isolated and characterized by 13C NMR was an oligomer of acrylonitrile attached to hexa(β-cyanoethyl)cyclopentadiene; the anion (at a β-alkyl position) of the latter apparently acted as anionic initiator. Attempts to induce thermal polymerization and cyclotrimerization of the pendent cyano groups of hexa(β-cyanoethyl)cyclopentadiene were unsuccessful even with added Lewis acid catalysts. Reduction to the hexaamine was only partially successful.
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  • 32
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    Polymer bulletin 27 (1992), S. 407-411 
    ISSN: 1436-2449
    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: Summary Ternary catalyst systems for the polymerisation of 1,3-butadiene to high cis content were studied. The systems Nd(carboxylate)3/tert-butyl chloride/diisobutylaluminium hydride (carboxylate = naphthenate, versatate) were studied with respect to the order of catalyst component addition on catalyst activity and polymer characteristics. Stable catalysts which give relatively narrow molecular weight distribution are give by component addition order Nd(carboxylate)3+diisobutylaluminium hydride+tert-butyl chloride. Less stable systems giving broader polymer molecular weight distributions are given by addition orders tert-butyl chloride+diisobutylaluminium hydride+Nd(carboxylate)3 and Nd(carboxylate)3 +tert-butyl chloride+diisobutylaluminium hydride.
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  • 33
    ISSN: 1436-2449
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    Notes: Summary The present study describes the preparation of polyorganosiloxanes containing dialkylaminopyridines in their side chains (POS-DAAPs) and the use of them as catalysts for esterolyses of p-nitrophenyl esters of CH3(CH2) n COOH (n=0–5). The POS-DAAPs (4, 5) were prepared from poly[(3-chlorocarbonylpropyl)methylsiloxane] (PCCPMS, 1) and two pyridine derivatives, such as 4-[(2-hydroxyethyl)methylamino]pyridine (HEMAP, 2) and 4-[4-(2-hydroxyethyl)piperidino]pyridine (HEPP, 3). Pyridyl groups of POS-DAAPs 4 and 5 were partially quaternized with dimethylsulfate (6, 7) in order to carry out esterolysis in homogenious systems. The esterolyses were examined in methanol/tris(hydroxymethyl)-aminomethane-hydrochloric acid buffer solution (vol. ratio 2/1, pH of buffer solution: 7.5) and analyzed following Michaelis-Menten like kinetics. The second-order rate constants (k 2/K m) of the esterolyses catalyzed by POSs 6 and 7 were 22–38 fold values of those catalyzed by the corresponding monomolecular catalysts 2 and 3. In addition, the effects of POSs were discussed from the kinetic, thermodynamic, and activation parameters.
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    Notes: Summary Copolymerizations of styrene and methyl methacrylate (MMA) have been carried out with azo-bis-(methyl isobutyrate-α-13C) (AIBMe-α-13C) as initiator and in the presence of ethyl aluminium sesquichloride (EASC). The specificity of the 1-methyl-1-(methoxycarbonyl)ethyl radical (I) for reaction with styrene over MMA is substantially enhanced by the presence of very low concentrations of EASC. This behaviour is consistent with the involvement of a complexes radical and suggests that such species may play an important role in Lewis acid induced alternating copolymerization.
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    Polymer bulletin 27 (1992), S. 429-434 
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    Notes: Summary The model compound 1,4-bis(anisylimido)benzene has been characterized by solution and CP/MAS 13C NMR to assist in the characterization of liquid crystalline polyazomethines (PAM) based on the same mesogenic structure. Thermal behavior of several homologs of this PAM series have been compared before and after treatment with the end capping agent benzaldehyde. The results suggest that PAM oligomers containing large quantities of amine termination can strongly effect thermal behavior at constant oligomer molecular weight.
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  • 36
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    Notes: Summary A low temperature ESR technique has been developed for the observation of free radical intermediates generated in clear polymer films during photolysis by UV light under nitrogen. The technique is simple and reproducible, and can be used for polymers having glass transition temperatures at or about room temperature without the need to employ spin traps. The generation of free radicals can be monitored and quantified during exposure, and the radical yields obtained can then be correlated with the chemical structure of the polymer to provide a rapid predictive evaluation of the exterior durability of the polymer.
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    Notes: Summary Electrical conductivities and ESR spectra were obtained for polyaniline salts that contained different counter anions. The electrical properties were markedly different from one salt to another, although the concentrations of counteranions were almost identical. The ESR spectra showed that different types of unpaired electrons were created upon protonation. There was a close correlation between the charge-transport property and the nature of unpaired electrons created upon protonation.
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    Notes: Summary Multicomponent intermacromolecular complexes have been prepared from some typical phenolic copolymers with a non-ionic polymer (e.g. PVP), and a polyelectrolyte (e.g. PAA). Some transition metal ions (e.g. Cu(II) and Ni (II)) have been incorporated in the complex through its unreacted co-ordinating groups. The formation of these complexes has been studied by several techniques, such as viscometry, conductometry, potentiometry, IR and UV spectrophotometry. A scheme has been presented to explain the mode of interaction of the various components.
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    Polymer bulletin 27 (1992), S. 577-583 
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    Notes: Summary The swelling and mechanical behaviour of networks of copolymers of acrylamide, methylenebisacrylamide and sodium 2-(2-carboxybenzoyloxy)ethylmethacrylate (mole fraction of salt x s =0–0.2) in water-acetone mixtures was investigated. In the range x s ≥0.01 phase transition (collapse) was observed, with both the extent of the collapse and the critical acetone concentration in the mixture at collapse, a c , increasing with increasing concentration of the salt. A comparison between these results and those obtained for networks with a quaternary ammonium salt led to a conclusion that an exchange of the positive charge of the ammonium salt (N⊕Cl⊖) for the negative charge of the sodium salt (COO⊖Na⊕) in the side chain decreases the critical content of salt necessary for the collapse, X s c , from 0.03 to 0.01, and the collapse takes place at lower concentrations of acetone. The collapse may also take place in a mixed solvent waterethanol; the dependence of network swelling on the concentration of ethanol is roughly the same as that on the concentration of acetone.
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    Polymer bulletin 27 (1992), S. 607-613 
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    Notes: Summary Polysilanes containing cyclodisilazane units in the backbone were synthesized by the modified Wurtz-type coupling of available dichlorosilanes with N,N′-bis (chlorodimethylsilyl)tetramethylcyclodisilazane in the mixture of solvents. The effect of solvent additives on the polymerization process was examined. These polymers are soluble in common solvents and very easily handled by molding or casting.
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  • 41
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    Notes: Summary A triblock copolymer of isotactic(it)-poly(methyl methacrylate) (PMMA) and polyisobutylene (PIB), it-PMMA-block-PIB-block-it-PMMA, was prepared by anionic polymerization of triphenylmethyl methacrylate initiated with α, ω-dilithiated PIB diisobutyrate in tetrahydrofuran at -78°C, and subsequntt hydrolysis and methylation with diazomethane. Molecular weight distribution of the triblock copolymer was narrow, and the stereoregularity of the PMMA block was highly isotactic. Proton spin-lattice relaxation times of the block copolymer in acetone-d6, which is non-solvent for PIB but dissolves the block copolymer, indicate the aggregation of the copolymer through PIB block. Stereocomplex formation between the it-block copolymer and syndiotactic(st)-PMMA-block-PIB-block-st-PMMA was also studied.
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  • 42
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    Notes: Summary The synthesis and thermal degradability of poly (DL-lactide) were investigated. Key factors affecting the polymer molecular weight were found to be monomer recrystallization, initiator concentration and the vacuum level during drying/sealing of the polymerization reaction ampoule. It was found that poly (DL-lactide) is thermally unstable above its melting temperature. Monomer recrystallization, polymer precipitation and a low initiator content of the polymer significantly inhibited the rate and extent of thermal degradation.
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    Polymer bulletin 27 (1992), S. 631-636 
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    Notes: Abstract The living carbocationic polymerization (LC⊕ Pzn) of p-methylstyrene (pMeSt) was achieved by the use of the 2-chloro-2,4,4-trimethylpentane (TMPCl)/TiCl4 initiating system in the presence of triethylamine (Et3N) electron donor in CH3Cl/nC6H14 mixed solvent at-80°C. Next, the synthesis, characterization, and some physical-mechanical characteristics of a series of poly (p-methylstyrene-b-isobutylene-b-p-methylstyrene) (PpMeSt-PIB-PpMeSt) triblocks is described. The latter synthesis involved two steps in one reactor: 1) The generation of diliving polyisobutylene dications (⊕PIB⊕) by the dicumyl chloride (DiCumCl)/TiCl4 system under similar conditions followed by 2) The addition of pMeSt and growth of living PpMeSt⊕ cations. The PpMeSt-PIB-PpMeSt triblocks are soft thermoplastic elastomers (TPEs).
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    Polymer bulletin 29 (1992), S. 119-126 
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    Notes: Summary Polysquaraines and polycroconaines have been synthesized. They form a new class of polymers with a small band gap, down to 0.5 eV. The small gap arises from the regular alternation of strong donor and acceptor-like moieties in a conjugated backbone.
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    Polymer bulletin 29 (1992), S. 135-138 
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    Notes: Summary Propylene oligomers with primary-OH, tertiary-0H andα,β-di-OH end groups have been prepared by converting the isopropenyl-ended oligomers with hydroboration-oxydation, oxymercuration-demercuration and performic acid hydroxylation reactions, respectively.
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    Polymer bulletin 29 (1992), S. 127-134 
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    Notes: Summary Kinetics of polymerization has been studied in the system isobutylene/dicumylmethylether/BCl3 (CH2Cl2, −80°C) in the presence of dimethyl sulphoxide added as electron donor in a broad concentration range. The apparent propagation rate constant showed a DMSO concentration dependence typical for complex equilibria. At a given DMSO concentration, the apparent rate constant decreases with increasing initial monomer concentration showing a seemingly zero-order propagation. A possible explanation of this phenomenon is the formation of a chain-end/monomer complex. Equilibrium and propagation rate constants have been determined.
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    Polymer bulletin 29 (1992), S. 343-348 
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    Notes: Summary In this technique, a relatively unreactive substance is transformed into a catalytically-active one within a protective environment. In this illustrative case, nickel formate was dissolved in a solution of poly(ethylene oxide) (PEO) in ethylene glycol, and then thermally decomposed in-situ to form finely-divided nickel particles. The mixture was dried, thereby protecting the nickel by encapsulating it in the polymer matrix. The distribution and the dispersity of nickel particles were investigated by electron microscopy. Upon adding portions of the catalyst-containing polymer to a reaction medium, the protective polymer dissolves, which releases the nickel particles and permits them to catalyze the reaction. In this particular case, the Ni-PEO sample was evaluated for the hydrogenation of an olefin, and found to be a highly efficient catalyst.
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  • 48
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    Notes: Summary The substitution patterns of methyl cellulose as well as of a thexyldimethylsilyl cellulose after permethylation were determined by hydrolysis and separation of the resulting partially methylated glucoses without further derivatization by h.p.l.c.. On an amine-modified silica column the solutes get separated into glucose, 2,3,6-tri-O-methyl glucose and the groups of mono-O-methyl-and di-O-methyl glucoses. A chromatographic run on a reversed-phase column enables the identification of the single mono-O-methyl- and di-O-methyl glucoses. In this way, a determination of both the average degree of substitution and the substitution pattern of cellulose derivatives is possible. Comparison of the results with those obtained by standard methylation analysis including g.l.c.-m.s. proves the correctnes of the method employed.
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    Polymer bulletin 29 (1992), S. 357-363 
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    Notes: Summary The kinetics of the reaction between a styrene-maleic anhydride copolymer (SMA) and amines was investigated in tetrahydrofuran solution between 0°C and 40°C. This reaction converts the maleic anhydride (MA) into the corresponding amide-acid, while the consecutive reaction of the generated acid with amine forming a diamide or transformation of the acid-amide into the imide was not observed. The amine reactivity follows the order: 1-octylamine〉 〉1-methyl hexylamine〉 〉1,1-dimethyl propylamine or dibutylamine, demonstrating that the amine reactivity depends, to a large extent, upon its steric hindrance. This reaction is reversible as shown by IR at high temperatures, but the reverse reaction was undetectable between 0 and 40°C. The overall reaction involves spontaneous and autocatalytic reactions, and the overall reaction rate can be written as:-d[MA]/dt=k0[MA][-NH2]+k1[MA][-NH0]2. In the case of 1-octylamine below 0.02 M, the spontaneous reaction dominates (i.e, k0〉 〉k1[-NH2]).
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    Polymer bulletin 29 (1992), S. 369-375 
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    Notes: Summary The chemiluminescence (CL) of polyethylene (PE) film induced by UV irradiation was investigated. CL parameter, I0, which indicates the oxidation rate under UV irradiation was obtained from a kinetic analysis. The I0 was found to be valuable to evaluate the durability of PE films.
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    Notes: Summary The effect of side chain length on intramolecular triplet energy migration of naphthalene containing polymers was investigated by a delayed fluorescence (DF) spectroscopy for the solid solution of the polymers. The degree of triplet energy migration depends strongly on whether the chromophores are directly attached to the main chain or not.
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    Polymer bulletin 29 (1992), S. 377-384 
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    Notes: Summary The 300 MHz1H-nmr spectra of poly(5-bromo-2-vinylthiophene) and poly(4-bromo-2-vinylthiophene) are presented and analyzed in terms of polymer stereochemistry. In both cases, the spectra could be explained in terms of the polymers having a Bernoullian, atactic stereochemistry.
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    Polymer bulletin 29 (1992), S. 385-392 
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    Notes: Summary The absolute rate constant of propagation (kp) in styrene polymerization was determined on the basis of ESR detection of the polymer radical in the temperature range of 0 to 130°C. The Arrhenius plot of kp gave a good linear relationship and the activation energy of the propagation was evaluated to be 39.7 KJ/mol. The termination rate constants over the same temperature range were also obtained by using the kp values according to the standard kinetics of radical polymerization. Apparent activation energy of the termination was estimated to be 15.6 KJ/mol.
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    Polymer bulletin 29 (1992), S. 595-595 
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    Polymer bulletin 29 (1992), S. A3 
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    Polymer bulletin 29 (1992), S. 587-594 
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    Notes: Summary The elastic modulus of polyacrylamide-acrylic acid hydrogels is studied in a wide range of swelling degrees. The modulus does not follow the concentration dependence predicted by the rubber elasticity theory. At low swelling degrees this can be attributed to the constrained state (non-phantom behaviour) of the network chains. The reason for the increase of modulus at nigh swelling degrees is seen in the finite extensibility and topological entanglements of the chains. A theory including these effects is proposed and verified by experiment.
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    Polymer bulletin 29 (1992), S. 597-603 
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    Notes: Summary Dehalogenation polycondensation of 1,4-diiodo-1,3-cyclohexadiene with zerovalent nickel complex gives a new π-conjugated polymer, poly(1,3-cyclohexadiene-1,4-diyl) PCyh. A copolymer constituted of 1,3-cyclohexadiene-1,4-diyl and 1,4-cyclohexadiene-1,4-diyl is also obtained by a similar method. The black color of PCyh indicates the presence of extensive π-conjugation along the polymer chain presumably due to takings-trans conformation of PCyh. PCyh is unstable and oxidized under air. IR and CP-MAS13C-NMR spectra of PCyh are reasonable for the structure.
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    Notes: Summary A fluorinated maleimide has been prepared from fluorinated diol with monofluoronitrobenzene. All the intermediates have been perfectly characterized by N.M.R. The study also describes the synthesis of a copolymer from a commercial vinyl ether and this maleimide. Copolymerization is not perfectly alternated as we could expect but the copolymer exhibits a glass transition equal to 165°C.
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    Polymer bulletin 29 (1992), S. 617-624 
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    Notes: Summary Organoboron polymers were prepared by hydroboration polymerization between various dienes and thexylborane. These polymers were reacted with α-furyllithium followed by the treatment with acetic acid and then by the oxidative treatment to give the corresponding polyalcohols having primary and tertiary hydroxyl groups. The structures of the polyalcohols obtained were characterized by1H-NMR compared with that for model compound, which was prepared by the reaction of dioctylthexylborane with α-furyllithium. These conversions from organoboron polymers to polyalcohols include the migrations of two polymeric chains from boron atom to carbon and the ring-opening of furan ring.
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    Polymer bulletin 29 (1992), S. 613-616 
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    Notes: Summary We describe the synthesis of monodisperse prepolymers containing one or two blocked isocyanate groups on the chain extremities. The prepolymers containing blocked isocyanate in one end and hydroxyl group in the other end are obtained by chemical transformation of undecylenic acid to acid chloride. This later was converted to the isocyanate by the CURTIUS reaction and blocked with nonyl-phenol. Finally the blocked isocyanate was telomerized with mercapto-ethanol. The resulting product is deblocked at T=105°C. By action of pure 2.4 T.D.I. (Tolylene diisocyanate) on the later product, we obtain a product containing blocked isocyanate end groups. The removal of the blocking agent could be effected at 100°C or less depending on the compound used to remove the blocking agent (amine).
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    Polymer bulletin 29 (1992), S. 625-632 
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    Notes: Summary Cyclopolymerization was carried out by various catalyst systems. MoCl5-based catalyst systems are more effective for the polymerization of 4,4-diphenoxy-1,6-heptadiyne than WCl6-based catalyst systems. Polymerization of 4,4-diphenoxy-1,6-heptadiyne leads to soluble, purple colored polymer with number average molecular weight (Mn) of 3.6x104-5.2x104.1H- and13C-MNR, IR,and UV-visible spectra of the resulting polymer indicated that poly(4,4-diphenoxy-1,6-hepatadiyne) possesses a polyene structure presumably with cyclic recurring units in the polymer backbone. Poly(4,4-diphenoxy-1,6-heptadiyne) had good thermal and oxidative stability, and good solubility in organic solvents. The electrical conductivity of iodine-doped polymer was 10−3-10−2 S/cm.
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    Polymer bulletin 29 (1992), S. 633-638 
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    Notes: Summary PET oligomers with different degrees of polymerization containing PHB as end groups were synthesized by melt condensation of bis(2-hydroxyethyl) terephthalate (BHET) in the presence of ethylp-hydroxybenzoate (EtPHB). Coupling the oligomers with terephthaloyl chloride, a series of block copolymers with identical triad aromatic ester “hard” segments as mesogen and different lengths of PET “soft” segments as spacer were obtained. Observation with a cross-polarized optical microscope shows that these copolymers are thermotropic in a certain range of the spacer length (n). Asn increases, the melting point (Tm) of the copolymer also increases, following the increasing molecular weight. The isotropic transition temperature (Ti) and the LC phase range (ΔT), on the other hand, decrease with the increasingn. Whenn exceeds a critical value, the LC phase disappears.
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    Polymer bulletin 29 (1992), S. 647-652 
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    Notes: Summary A method is described for determining the absolute rate constants for the first few propagation steps in radical polymerization. The procedure involves a product analysis of the oligomeric alkoxyamines formed when an initiator is decomposed in monomer containing a very low concentration of a nitroxide radical scavenger. The method is illustrated with analysis of data for methyl acrylate. The rate constants for the first two propagation steps for polymerization of this monomer,k p(1) andk p(2), are at least an order of magnitude greater thank p(average). Values of the absolute rate constants for reactions of phenyl and primary alkyl radicals with methyl acrylate are also estimated.
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    Notes: Summary Ethylene and propylene co-polymerization and sequential polymerization with high activity supported titanium catalysts were studied. Specific rate of homopolymerization and copolymerization constants for ethylene and propylene were determined by using the derived values of the solubility constants for monomers in nascent polymers. The reason of the increased rate of co-polymerization upon enriching the monomers mixture with propylene, the effect of activation of ethylene polymerization upon preliminary polymerization of propylene may be in the increasing number of active sites due to enlarged content of amorphous phase in the nascent polymer product.
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    Rheologica acta 31 (1992), S. 83-93 
    ISSN: 1435-1528
    Keywords: Capillary rheometer ; xanthan solutions ; Bagley correction ; slip development
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract Flow experiments through capillaries with 0.2% xanthan in aqueous solution and 0.1 N NaCl brine were carried out to study the influence of the molecular conformation on the flow development at relatively low shear rates, from 20s−1 to 400s−1. Capillaries with a wide range of length-to-diameter ratios, L/D = 4.5 to 1015 were used. The apparent viscosity as a function of L/D at a constant shear rate shows a continuous decrement of the viscosity as L/D increases, until an asymptotic value is reached. The decrement in the apparent viscosity is partially explained in terms of slip. It was found that slip is a function of L/D as well as shear stress, i.e., slip develops during flow, thus inducing spatial anisotropy in the fluid until a stable state is reached. However, the substantial difference in apparent viscosity between short capillaries and capillaries longer than 300 D may be attributed to dominant elongational flow due to the contraction in the small capillaries and slip in long capillaries. The flow in a sufficiently long capillary can be divided in four regions rather than three, as is usually assumed. In the first region, which corresponds to the entry, elongational and shear flow coexist and elongational flow dominant. In the second region, end effects and slip development are coupled. In the third region the flow is fully developed and end effects are negligible. However, the fluid shows physical characteristics different from those of the fluid at rest, as a consequence of prior slip development. The fourth zone is the exit region in which the velocity rearranges due to the change of boundary conditions. The length of each region depends on the conformation of the macromolecules and shear rate. In addition, it was found that the stiffness of xanthan increases with the increase of the ionic strength. Finally, a performance of Bagley's analysis in the whole range of L/D studied showed that the use of the Bagley correction is not a reliable way to correct for end effects when the flow is not fully developed and/or in the presence of slip.
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  • 66
    ISSN: 1435-1528
    Keywords: Viscoelastic fluid ; relaxation spectrum ; retardation spectrum ; Tikhonov regularization
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract The application of Tikhonov regularization to the determination of relaxation and retardation spectra of viscoelastic fluids is discussed using simulated and real experimental data. It is thereby shown that with this method consistent results for relaxation and retardation spectra can be obtained from experimental data for different material functions. Furthermore, the differences between the most frequently used variants of Tikhonov regularization and the maximum entropy method are discussed. For most calculations the program FTIKREG has been used, which is an especially fast and reliable implementation of Tikhonov's regularization method.
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  • 67
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    Rheologica acta 31 (1992), S. 194-205 
    ISSN: 1435-1528
    Keywords: Superimposed oscillatory shear ; complex shear modulus ; torsion pendulum ; nearly viscometric flow
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract To investigate the viscoelastic behavior of fluid dispersions under steady shear flow conditions, an apparatus for parallel superimposed oscillations has been constructed which consists of a rotating cup containing the liquid under investigation in which a torsional pendulum is immersed. By measuring the resonance frequency and bandwidth of the resonator in both liquid and in air, the frequency and steady-shear-rate-dependent complex shear modulus can be obtained. By exchange of the resonator lumps it is possible to use the instrument at four different frequencies: 85, 284, 740, and 2440 Hz while the steady shear rate can be varied from 1 to 55 s−1. After treatment of the theoretical background, design, and measuring procedure, the calibration with a number of Newtonian liquids is described and the accuracy of the instrument is discussed.
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    Rheologica acta 31 (1992), S. 264-273 
    ISSN: 1435-1528
    Keywords: Flow stability ; Couette flow ; Taylor vortices ; power law viscosity
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract The stability of the Couette flow of the liquid with the power law viscosity in a wide annular gap has been investigated theoretically in this work with the aid of the method of small disturbances. The Taylor number, being a criterion of the stability, has been defined using the mean apparent viscosity value in the main flow. In the whole range of the radius ratio, R i /R o and the flow index, n, considered (R i /R o ≥ 0.5, n = 0.25–1.75 ), the critical value of the Taylor number Ta c is an increasing function of the flow index, i.e., shear thinning has destabilizing influence on the rotational flow, and dilatancy exhibits an opposite tendency. In the wide ranges of the flow index, n 〉 0.5, and the radius ratio, R i /R o 〉 0.5, the wide-gap effect on the stability limit is predicted to be almost the same for non-Newtonian fluids as for Newtonian ones. The ratio on the critical Taylor numbers for non-Newtonian and Newtonian fluids: Ta c (n) and Ta c (n = 1) obey a generalized functional dependence: Ta c (n)/Ta c (n = 1) = g(n), where g(n) is a function corresponding to the solution for the narrow gap approximation. Theoretical predictions have been compared with experimental results for pseudoplastic liquids. In the range of the radius ratio R i /R o 〉 0.6 the theoretical stability limit is in good agreement with the experiments, however, for R i /R o 〈 0.6, the critical Taylor number is considerably lower than predicted by theory.
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  • 69
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    Rheologica acta 31 (1992), S. 309-322 
    ISSN: 1435-1528
    Keywords: Linear-viscoelasticity ; material functions ; rheological constitutive equation ; fractional derivative
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract Starting from an analysis of the rheological behavior of the complex modulus predicted by the Cole-Cole formalism, a generalized Cole-Cole ansatz is suggested in order to overcome the related difficulties. The corresponding rheological constitutive equation with fractional derivatives belonging to the generalized Cole-Cole respondance is stated and the characteristic material functions of the linear viscoelasticity theory (like the dynamic modulus and compliance, the relaxation and ratardation functions, the spectra, etc.) are derived. Model predictions of these functions will be compared with experimental results from dynamical measurements and creep data on different polymer systems which show cooperative phenomena (polymeric glasses and gelling systems). One can see that the modified ansatz fits the data very well, in spite of its relative simplicity.
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    Rheologica acta 31 (1992), S. 3-13 
    ISSN: 1435-1528
    Keywords: Liquid ; non-Newtonian liquid ; constitutive equation ; principal stretches
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract The K-BKZ constitutive equation for non-Newtonian liquids usually uses as invariants the coefficients of the characteristic equation of a certain finite strain tensor. We show that the use of the roots of this equation, the squares of the principal stretches, is more efficient. We use a product of the linear relaxation spectrum and a simple sum of powers of the principal stretches as the “energy function” in the K-BKZ theory. The predictions of this theory agree with Meissner's data to a good approximation over many decades.
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    Rheologica acta 31 (1992), S. 44-54 
    ISSN: 1435-1528
    Keywords: Rigid polyvinyl chloride (PVC) ; constitutive equations ; recoil
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract Polyvinyl chloride (PVC) is widely used in industry, but it is difficult to find any extensive discussion of theological relations that describe it. The present paper discusses the behaviour of rigid PVC in extensional deformations at various temperatures. In the tests, a step elongation was applied at an initial time, then after a delay the specimen was cut, permitting recoil. Both linear and nonlinear strain regimes were studied; the linear relaxation properties (relaxation function, storage modulus) were cross-checked with eccentric-disk measurements. In the non-linear strain regime a single-integral constitutive equation of the KBKZ Wagner type was used. Separability of time and strain effects was demonstrated in our tests and so a “damping function” could be found which was only a function of strain. Video recordings of recoil were made, and detailed predictions of the strain-time behaviour were checked against experiments. Various constitutive equation proposals were used in the comparison, and the separated kernel integral irreversible model performed reasonably well; some other models of a differential type, and a Doi-Edwards model were not as accurate.
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  • 72
    ISSN: 1435-1528
    Keywords: Suspension theology ; spheroid ; Brownian diffusion
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract Suspensions of small nonspherical particles having dipolar moments exhibit non-Newtonian behavior under the influence of shear and external fields. Numerical methods are presented for calculating the rheological and rheo-optical properties of dilute suspensions of Brownian particles having permanent dipoles subject to time-dependent shear and external fields. The numerical methods employ the Galerkin method of weighted residuals to solve the differential equation for the particle orientation distribution function. The steady-state shear flow intrinsic viscosity of suspensions of particles with sufficiently extreme aspect ratio is predicted to exhibit a maximum value attained for intermediate shear rates at selected field orientations. These numerical results provide valuable insight into the coupling which occurs between the effects of rotary Brownian motion, the hydrodynamic resistance of nonspherical particles, and the external torque exerted on dipolar particles. The results are applicable to both suspensions of magnetic particles and electrically dipolar particles.
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  • 73
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    Rheologica acta 31 (1992), S. 151-160 
    ISSN: 1435-1528
    Keywords: Radiation cross-link ; ultraviolet radiation ; gelation
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract Ultraviolet-radiation-cured cross-linked systems are used extensively in optoelectronic applications. We describe a new in situ technique for doing controlled curing of photosensitive materials and monitoring the gelation through dynamic theological measurements. In this method, a sample placed between quartz windows of a modified parallel plate fixture of a Rheometrics Mechanical Spectrometer is radiated from a collimated UV source using a liquid light guide and a mirror. By varying the sample exposure to UV radiation, the degree of cross-linking can be precisely controlled to observe the material behavior in the pre, post, and critical gel state. Time-dependent measurements on urethane based materials show the gelation behavior to have an “induction” period with no change in dynamic moduli (G′, G″), followed by their sharp increase as the materials develop a network structure. The critical gel point is characterized by a power-law dependence of the dynamic moduli on frequency. The gelation kinetics scales with sample thickness and radiation intensity, the scaling factor in both cases being the critical gelation time. The rheological measurements correlate with differential photocalorimetric studies.
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    Rheologica acta 31 (1992), S. 413-420 
    ISSN: 1435-1528
    Keywords: Interfacial stability ; viscoelastic fluids ; plane Poiseuille flow ; multiphase flow ; elastic instability
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract Purely elastic interfacial stability of superposed plane Poiseuille flow of polymeric liquids has been investigated utilizing both asymptotic and numerical techniques. It is shown that these instabilities are caused by an unfavorable jump in the first normal stress difference across the fluid interface. To determine the significance of these instabilities in finite experimental geometries, a comparison between the maximum growth rates of purely elastic instabilities with instabilities driven primarily by a viscosity or a combined viscosity and elasticity difference is made. Based on this comparison, it is shown that purely elastic interfacial instabilities can play a major role in superposed flow of polymeric liquids in finite experimental geometries.
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  • 75
    ISSN: 1435-1528
    Keywords: Dynamicviscoelasticity ; polymersolution ; multiple lumpresonator
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract The Birnboim-Schrag multiple lumped resonator (MLR) is the most sensitive and precise instrument in existence for dynamic viscoelastic measurements on dilute low-viscosity polymer solutions in the frequency range 100–8000 Hz. Estimation of polymer viscoelastic spectra from MLR-data has so far been carried out using an approximate dumbbell theory for description of the torsional dynamics of the resonator itself. Here, we report on the development of a significantly improved mathematical description of the resonator dynamics in the absence and presence of surrounding polymer solution. For some of the lumps the relative torsional displacements predicted by dumbbell theory and the new analysis differ by as much as a factor of 2. In an accompanying paper, we show that the predictions of our new theoretical analysis is in excellent agreement with experimental measurements of resonator dynamics. The new analysis does not rest on any particular choice of number of lumps, relative lump size, which lumps are surrounded by polymer solution, or the length or the diameter of each torsional spring. The mathematical analysis takes fully into account the mass and the energy loss of each torsional spring as well as the mechanical coupling between each spring and the surrounding medium. This part of the analysis is carried out in terms of damped torsional waves. An analytical analysis in terms of normal modes as well as the results of numerical analysis of the full set of simultaneous differential equations describing the resonator torsional dynamics are presented. The relationship between idealized dumbbell theory and normal mode theory is discussed. We also demonstrate how more accurate estimates of the viscoelastic parameters for polymers from experimental data can be obtained using the improved theory.
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  • 76
    ISSN: 1435-1528
    Keywords: Complexviscosity ; dynamicviscometer ; rheometer ; triblockcopolymer ; transducer
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract A dynamic viscometer is described, with which the dynamic moduli in the frequency range from 2 × 10−3 to 10 Hz can be determined for liquids with 10−3 Pa〈 |G * | 〈102 Pa. Due to the application of an air bearing and inductive transducers for the detection of the angular displacement of both the drive and the measuring cylinder a sensitive apparatus has been made. Very small strains (γ0 ≅ 10−3) can be applied and only a small amount of sample (4 ml) is needed. The operation of the apparatus is fully computer-controlled, thus, long runs at various frequencies and temperatures are possible without operator intervention. The theoretical background, calibration procedure, and operation window are described. A presentation of some measurements on two polyisoprene/polystyrene triblock copolymer solutions concludes the work.
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    Rheologica acta 31 (1992), S. 592-602 
    ISSN: 1435-1528
    Keywords: Injection molding ; viscous dissipation ; solidified layer ; diffusion equation
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract An analytical solution is obtained for the stationary temperature profile in a polymeric melt flowing into a cold cavity, which also takes into account viscous heating effects. The solution is valid for the injection stage of the molding process. Although the analytical solution is only possible after making several (at first sight) rather stringent assumptions, the calculated temperature field turns out to give a fair agreement with a numerical, more realistic approach. Approximate functions were derived for both the dissipation-independent and the dissipation-dependent parts which greatly facilitate the temperature calculations. In particular, a closed-form expression is derived for the position where the maximum temperature occurs and for the thickness of the solidified layer. The expression for the temperature field is a special case of the solution of the diffusion equation with variable coefficients and a source term.
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  • 78
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    Rheologica acta 6 (1967), S. 74-76 
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    Rheologica acta 6 (1967), S. 30-53 
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    Notes: Summary Measurements of the isothermal-isobaric volume retardation in crosslinked and non-crosslinked polystyrene are reported. The measurements have been carried out applying the temperature-jump method, and, for the first time, also the pressure-jump method. For the measurements using the temperature-jump method a quartz-glassdilatometer has been used which allows the registration of volume changes of ±7·106 cm3. A pressure dilatometer has been developed for the measurements according to the pressure-jump method which permits volumemeasurments of the same precision in the pressure-range between 1 and 60 atmospheres. The experimental results show that for the volume retardation of polystyrene a measurable linear region exists. For this case of linear retardation behaviour various kinetic theories predict an exponential time dependence of the deviation of the volume from the equilibrium value, which is due to the existence of a single retardation time. This result is not confirmed by our experiments. The volume retardation in the linear region — at least for polystyrene — can in no case be described in terms of a single retardation time, but only by a distribution of retardation times. It turns out, that the retardation function (distribution function of retardation times) in the linear region differs after a previous temperature change from that after a previous pressure change. This result can be confirmed by theoretical considerations which follow fromMeixner's thermodynamic theory of linear relaxation phenomena.
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    Rheologica acta 6 (1967), S. 65-69 
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    Notes: Résumé Le comportement en viscosité sous différentes vitesses de cisaillement, à différentes températures, de solutions d'alginate de sodium à des concentrations variant entre 0,05% et 1%, auxquelles on a ajouté du chlorure de calcium en quantité variable, est qualitativement toujours le même; pour des quantités croissantes de chlorure de calcium, à concentration fixe en alginate de sodium, à une phase de dépression de la viscosité succède une phase de croissance très rapide, suivie à nouveau d'une phase de décroissance. Dans la première phase les variations de la viscositè avec la vitesse de cisaillement sont représentables par un modèle répondant à la Théorie d'Eyring; dans les phases suivantes l'écoulement est représenté par une loi du type η=aγb avec b〈0. Cette différence dans le mode d'écoulement tiendrait à l'apparition, à partir d'une concentration en chlorure de calcium suffisante, d'une structure tridimensionelle plus ou moins stable suivant la concentration en ions calcium.
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    Rheologica acta 6 (1967), S. 83-92 
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    Notes: Zusammenfassung Eine Versuchsanordnung wird beschrieben, in derSearle- undCouette-Typ des Rotationszylinderviskosimeters durch leichten Umbau zu erhalten sind. Für alle Fälle (Außen- und Innenzylinder desSearle- undCouette-Viskosimeters) werden die Drehmomente in Abhängigkeit von der exzentrischen Stellung der Zylinderachsen für mehrere Drehzahlen und Zylinderlängen bestimmt. Alle von der Theorie vonW. Müller über die Drehmomente gelieferten Aussagen lassen sich demonstrieren und in verhältnismäßig weiten Bereichen quantitativ belegen. Es werden die Möglichkeiten behandelt, wie die im Einzelfall nur mühsam zu berechnenden Beiwerte leicht zugänglich bereitzustellen sind.
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    Rheologica acta 6 (1967), S. 92-100 
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    Description / Table of Contents: Summary Entangling and disentangling of chain-molecules give rise to an equilibrium concentration of entanglements and a time-law for the relaxation of momentarily strained pseudonetwork-chains. The network-chains in the middle of the molecules can only relax more slowly than those near the ends. This leads to distributions of strains during the flow. In case of large strains a network-chain must disentangle more quickly than in the unstrained state, which results in non-Newtonion viscosity and abnormally quick relaxation. Experiments confirm this theory to a large extent.
    Notes: Zusammenfassung Amorphe Polymere ausreichend hohen Molgewichts befinden sich in einem dynamischen Gleichgewicht der Verhakung ihrer Moleküle. Dabei diffundieren die Moleküle ständig mit ihren Kettenenden durch die Schlaufen der tetraederförmigen Verhakungen, lösen dabei eine Verhakung und bilden sofort wieder eine neue an anderer Stelle, so daß das MolgewichtM c der Kettenstücke zwischen den Verhakungsstellen zeitlich konstant ist. In der Nähe der Kettenenden werden Verhakungen häufiger gelöst und wieder gebildet als mehr in der Mitte der Fadenmoleküle. Dort bleiben deshalb Dehnungszustände der Kette länger erhalten als an den Kettenenden. Mit dieser Vorstellung kann man die mechanische Relaxation der Polymeren gut beschreiben. Man benötigt dazu außer dem Molgewicht drei Konstanten.-Beim Fließen der Polymeren werden die in der Mitte liegenden Kettenstücke wegen ihrer großeren Relaxationszeit stärker gedehnt als die am Kettenende liegenden Teile. Im Gleichgewicht stellt sich eine Dehnungsverteilung ein, mit der man dieNewton-Viskosität berechnen kann. Strukturviskosität tritt dann auf, wenn in der Dehnungsverteilung starke Dehnungen auftreten. Bei starker Dehnung löst sich ein Kettenstück schneller als normal aus seinen Verhakungen, weil es dann auf die Verhakungpunkte eine größere Kraft ausübt als in ungedehntem Zustand.
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    Rheologica acta 6 (1967), S. 119-129 
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    Notes: Summary A mechanical system consisting of an inert component, attached to a linear viscoelastic spring, is studied theoretically. Basic assumptions about the viscoelastic material areBoltzmann's superposition principle and a positive discrete relaxation spectrum. The equation of motion and its formal solution for free damped vibrations are discussed. The theory focusses on the determination of the complex dynamic modulus, defined for undamped sinusoidal vibrations, by free damped vibrations. Simple approximation formulae to calculate the dynamic modulus from free vibration data, i. e. eigen frequency and logarithmic decrement, are given; upper limits for the approximation errors could be derived.
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    Rheologica acta 6 (1967), S. 222-239 
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    Notes: Résumé Après un bref rappel des méthodes d'étude des matériaux bitumineux, suivi de la description des appareillages mis au point pour l'étude expérimentale du fluage, sont exposés les résultats des essais de traction et de cisaillement par torsion. Ces expériences, effectuées sur des éprouvette d'un béton bitumineux de type classique, mettent en évidence que: Le domaine de comportement linéaire du matériau est très restreint en ce qui concerne l'intensité de la contrainte appliquée ou la grandeur de la déformation. La réciprocité entre les rôles du temps et de la température dans la description des propriétés mécaniques du matériau est vérifiée. L'application de la méthode des variables réduites permet alors d'étendre les connaissances acquises, en dehors du domaine étudié. Les propriétés rhéologiques du matériau peuvent être présentées sous forme d'expressions analytiques simples. Il est aussi possible d'attribuer au matériau un modèle comprenant sept paramètres dont six d'entre eux sont indépendants de la température, le dernier ne dépendant que de la susceptibilité thermique du matériau La susceptibilité thermique elle-même peut être présentée sous forme analytique simple. L'étendue des recoupements qui peuvent être faits à partir des essais de fluage en traction et en torsion et la concordance des résultats obtenus par les méthodes statiques et dynamiques, mettent en évidence le caractère intrinsèque des informations acquises.
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    Rheologica acta 6 (1967), S. 246-251 
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    Notes: Summary Transient creep recovery tests in simple tension were performed in a series of cross-linked high polymers in pure and plasticized states. A loading cycle was adopted according to which each specimen was loaded in creep for a time period of 16′ followed by recovery for the same time period. This loading cycle was repeated for various steps of temperature from ambient temperature up to a temperature corresponding to the rubbery region of each polymer. It was shown that, while the 15″ measurements of deformation after loading or unloading were approximately equal, recovery individual curves were always lagging in time the corresponding creep curves. Composite curves of creep or recovery deformation in semi-log time scale reduced to a temperature of 30 °C were plotted by applying the method of reduced variables. The creepdeformation composite curve was always advancing in time relatively to the respective recovery composite curve. This phenomenon was an accumulation of the partial difference of the corresponding individual curves. Time-shift factor versus temperature curves for creep and recovery were plotted and compared. It was established that the remaining deformation after 16 minutes of a 16′ creep recovery normalized to the initial deformation at the beginning of recovery, if plotted versus temperature, presented the same shape of curves for all types of materials tested. The maxima of these curves were diminishing with addition of plasticizer according to a straight line.
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    Rheologica acta 6 (1967), S. 259-264 
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    Notes: Summary In order to investigate the thermal effects occuring in a coaxial cylinder viscometer, the temperature changes at the onset of the flow and the temperature profiles reached under steady-state conditions have been measured, at different radial positions, by means of an NTC resistor. The results have been found to agree satisfactorily with the equations developed for the theoretical description of the above effects.
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  • 88
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    Notes: Summary A typical property of greases, as plastic disperse systems, is their thixotropy (reversible destruction of their structure due to deformation). In relation to this, if the rate of their formation drops below a certain critical value it becomes practically very difficult or even impossible to attain steady conditions of their flow. This is observed both in rotational plastoviscometers and in rolling-contact bearings, and is manifested in more or less sharp fluctuations of the resistance moments. The critical value of the rate of deformation depends on the nature of the grease and the rigidity of the braking device or the power reserve of the drive, decreasing when these values are increased. When soap greases are deformed they become anisotropic, which, when the direction of deformation is changed, tells perceptibly on their resistance to deformation and results in fluctuations of the resistance moments in rolling bearings.
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    Rheologica acta 6 (1967), S. 284-288 
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    Notes: Summary The bahavior of granular materials in theMac Michael type viscometer was studied. The deflection angle of the bob decreased with the increase of the rate of rotation of the cup in the cases of these materials contrary to those of liquids. The powder bed in the gap of the viscometer is divided into twp cylindrical parts, the inner one with flowing layers of particles and the other moving with the cup as a bulk. The existence of these two parts is considered responsible for the extraordinary behavior of powder in the viscometer. The coefficient of kinetic friction of powder layers was obtained by applyingBenarie's analysis to our results.
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    Rheologica acta 6 (1967), S. 296-298 
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    Rheologica acta 6 (1967), S. 306-311 
    ISSN: 1435-1528
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Summary Consideration is given to the unsteady motion of a lamina moving under a constant force in an idealised elastico-viscous liquid contained between walls parallel to the lamina. It is shown that the velocity of the lamina is strongly dependent upon the elasticity of the liquid. Both the time at which the velocity of the lamina attains an effective steady value and the corresponding distance travelled by the lamina depend in a marked way upon an elastic parameterλ.
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  • 93
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    Rheologica acta 6 (1967), S. 323-330 
    ISSN: 1435-1528
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract An unusual stress controlled turbulent flow phenomenon observed in aqueous solutions of some derivatives of an unsaturated 18 carbon atom fatty acidis described. Some other unusual viscometric and rheogoniometric properties of these solutions are also discussed.
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  • 94
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    Rheologica acta 6 (1967), S. 316-323 
    ISSN: 1435-1528
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Summary A description is given of an instrument for the measurements of the dynamic shear modulus,G, and the corresponding damping, tanδ, of solid polymeric materials. The instrument is suitable for the measurement of moduli in the range from 106 to 1010 newton/m2, tanδ values from 0.005 to 3 and frequencies between 0.1 and 20 Hz. The temperature of the specimen can be adjusted to any value between −180 and + 300
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  • 95
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    Rheologica acta 6 (1967), S. 330-338 
    ISSN: 1435-1528
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 96
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    Rheologica acta 6 (1967), S. 171-173 
    ISSN: 1435-1528
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Zusammenfassung Beim Durchfluß von hochpolymeren Schmelzen durch ein elliptisches Rohr wurden Sekundärströmungen nachgewiesen. Das beweist, daß die untersuchten viskoelastischen Substanzen (Polyäthylen, Polystyrol, Polymethylmethacrylat) nicht zur Klasse derWeissenberg-Flüssigkeiten gehören.
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  • 97
    ISSN: 1435-1536
    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: Summary Films of polyethylene terephthalate drawn near the glass transition temperature show evidence of the development of stress-induced morphological alteration (referred to the amorphous, unoriented form) as deduced from observed initial increases in permeability and decreases in apparent permeation activation energy for oxygen. The respective values of $$\bar P$$ and $$E_{\bar P}$$ for the smaller molecule, helium, are less affected over the same range of film elongations. A simple two-group transport model of the polymer microstructure suffices to explain the data and electron micrographs reveal that an unusual type of crystalline phase, apparently the result of stretching nearT g , is the origin of the low activation energy pathways, leading to the observed diffusional enhancement for oxygen.
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  • 98
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    Colloid & polymer science 220 (1967), S. 159-168 
    ISSN: 1435-1536
    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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  • 99
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    Colloid & polymer science 220 (1967), S. 97-107 
    ISSN: 1435-1536
    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: Zusammenfassung Es wird über Messungen der Gasdurchlässigkeit von gummielastischen Werkstoffen für Stickstoff berichtet. Der Gasdurchtritt von Stickstoff durch gummielastische Materialien ist ein Permeations- oder Lösungsdiffusionsvorgang. Die Theorie der Permeation wird dargelegt, und zwei Methoden zur Auswertung von Permeationsmessungen werden angegeben. Nach Beschreibung der Meßanordnung wird an Hand von einigen grundsätzlichen Messungen der Gasdurchlässigkeit von gummielastischen Werkstoffen für Stickstoff gezeigt, daß es sich hier tatsächlich um einen Lösungsdiffusionsvorgang handelt; d. h. dasFicksche Diffusionsgesetz und dasHenrysche Löslichkeitsgesetz sind erfüllt, und die Diffusion ist der geschwindigkeitsbestimmende Vorgang. Die Betrachtung der Temperaturabhängigkeit der Permeation zeigt, daß man für Diffusionskoeffizient, Löslichkeitskoeffizient und Permeationskoeffizient jeweils eine Aktivierungsenergie angeben kann. Meßergebnisse, die an einer Vielzahl von gummielastischen Werkstoffen erhalten wurden, werden mitgeteilt.
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  • 100
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    Colloid & polymer science 220 (1967), S. 145-147 
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Summary In the 100-Mc/sec spectra of vinylidene chloridevinylacetate-copolymers lines of pentads (CH-resonance) and lines of hexads (CH2-resonance) are shown by spin-decoupling technique. The differences between these lines are strongly dependent on the type of solvent. The concentrations of pentads and hexads experimentally determined from the line intensities agree satisfactorily with the calculated values. In the calculations the parameters of copolymerizationr 1=5,00 andr 2=0,05 are used.
    Notes: Zusammenfassung In den 100-MHz-Spektren von Vinylidenchlorid-Vinylacetat-Copolymeren werden mit Spin-Entkopplung Pentadenlinien (CH-Resonanz) und Hexadenlinien (CH2-Resonanz) nachgewiesen. Die Abstände zwischen diesen Resonanzlinien hängen stark vom Lösungsmittel ab. Die experimentell aus den relativen Linienintensitäten gemessenen Pentaden-und Hexadenkonzentrationen stimmen mit berechneten Werten befriedigend überein. Bei der Rechnung wurden die Copolymerisationsparameterr 1=5,00 undr 2=0,05 zugrunde gelegt.
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