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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 56 (1997), S. 9-22 
    ISSN: 0006-3592
    Keywords: condensation reactions ; disaccharides ; equilibria ; glucoamylase ; kinetics ; monosaccharides ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Arabinose, fructose, galactose, myo-inositol, lyxose, mannose, ribose, and xylose were incubated individually and with glucose in the presence of Aspergillus niger glucoamylase at pH 4.5 and 45°C. Glucoamylase condenses galactose, glucose, and mannose individually into disaccharides. It also produces mixed disaccharides when each of the eight carbohydrates is incubated with glucose. Many products were identified by gas chromatography of the derivatized reaction mixtures followed by mass spectroscopy of the individual chromatographic peaks. Galacto-, gluco-, or mannopyranosyl rings appear to be present at the nonreducing ends of all the disaccharides produced. Molecules linked through primary hydroxyl groups have the highest equilibrium constants of all products formed, since these bonds are thermodynamically favored. However, glucoamylase is capable of forming bonds with many available hydroxyl groups, as previously demonstrated when it was incubated with glucose alone. Formation rates of different bonds linking different residues vary widely. These results demonstrate that glucoamylase has a wide selectivity toward residues it will condense into disaccharides and toward bonds it will form between them. © 1997 John Wiley & Sons, Inc. Biotechnol Bioeng 56: 9-22, 1997.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Cell Motility and the Cytoskeleton 30 (1995), S. 164-170 
    ISSN: 0886-1544
    Keywords: actin ; purification ; methods ; kinetics ; Cap Z ; chickens ; antibodies ; blotting ; immuno-affinity purification ; immunoabsorbance ; muscle proteins ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: Gel-filtration is commonly used to remove contaminants from conventional actin prepared by the method of Spudich and Watt. It has been shown that this procedure removes the majority of a factor that reduces the low-shear viscosity of actin. We have previously reported that this factor is Cap Z, a barbed end capping protein. We now establish that, even after gel-filtration, enough Cap Z can be present in conventionally prepared actin to affect events occurring at the barbed ends of actin filaments. We also demonstrate that the concentration of Cap Z can be reduced to more than a log below the KD for binding of Cap Z to actin by either (1) immunoabsorbtion of conventionally prepared actin with anti-Cap Z antibodies, or (2) an additional cycle of polymerization/depolymerization followed by repeat gel-filtration. © 1995 Wiley-Liss, Inc.
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 851-863 
    ISSN: 0887-624X
    Keywords: polymerization ; kinetics ; free radical ; transfer ; photolysis ; propagation ; rate coefficients ; termination ; EPR ; copolymerization ; initiation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The problems of determining reliable, well-characterized values of kinetic parameters in free-radical polymerizations are discussed. The origins of the fact that experimental determinations of rate coefficients of ostensibly identical systems often result in quite different values being reported can be ascribed to subtle mechanistic assumptions made in data interpretation, which are considered in detail. A series of recommendations to assist in overcoming these problems, and to highlight their origins, are presented, with emphasis placed on new techniques including those employing laser photolysis and EPR.
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  • 4
    ISSN: 0887-624X
    Keywords: heparin ; 2,4,6-trinitrobenzenesulfonic acid ; kinetics ; α-amino acid ; hexosamine residue ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of heparin with 2,4,6-trinitrobenzenesulfonic acid (TNBS) were studied spectrometrically. Seven different commercial heparins were used in this study. The amino groups react with TNBS to form equimolar amounts of trinitrophenylated (TNP) amino groups and bisulfite ions. The TNP-amino groups further react with bisulfite ions to form the monosubstituted anionic sigma complex. The absorption spectrum with two maxima at approximately 350 nm and approximately 420 nm, characteristic of either the TNP-amino groups or the complex, was analyzed for the reaction of TNBS with heparin. It was shown that the reactivities of TNBS with amino groups from α-amino acid and hexosamine residues are greatly different. By combining the results of the reaction kinetics and the reaction of heparin with Sanger's reagent, the number of the α-amino groups and the free amino groups in hexosamine residues were determined. These data have been performed with a range of heparins from different commercial sources, of different activities and physical characteristics. No correlation was found between the free amino contents of these heparins and biological potency. © 1993 John Wiley & Sons, Inc.
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  • 5
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 1007-1012 
    ISSN: 0887-624X
    Keywords: photopolymerization ; isatoic anhydride-Br2 ; kinetics ; free-radical ; nonideal ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Isatoic anhydride (IA) alone did not initiate photopolymerization of methyl metacrylate (MMA) at 40°C when exposed to visible light for about 180 min. But IA, when used in combination with bromine (Br2) as the initiator, initiated the photopolymerization of MMA readily under the same conditions. This behavior was explained by the formation of a donor-acceptor type of complex between IA and Br2 in the presence of MMA. The polymerization was found to proceed via a free radical mechanism and the radical generation process was considered to follow an initial complexation reaction between the initiator components and monomer. The complex initiator showed nonideal kinetics for the present system (initiator exponent 〈 0.5) and was analyzed. The monomer exponents varied from 0.83 to 1.15 normally depending on the nature of solvent used. Initiator-dependent chain termination was significant as well as the bimolecular mode of chain termination. © 1993 John Wiley & Sons, Inc.
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  • 6
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 691-700 
    ISSN: 0887-624X
    Keywords: monoesterification ; maleic anhydride copolymers ; catalysis ; kinetics ; chemical equilibrium ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A kinetic investigation on the monoesterification reaction of the maleic anhydride residue (MA) in styrene-maleic anhydride copolymers with aliphatic alcohols was carried out in ethyl benzene solution. By comparison to classic catalysts such as tributylamine (TBA) and pyridine, 4-dimethylaminopyridine (4DMAP) is by far the most effective catalyst for this reaction. While both general base and nucleophilic mechanisms contribute to the reaction catalyzed by TBA or pyridine, a nucleophilic mechanism prevails with 4DMAP. This reaction is reversible, and its chemical equilibrium constant decreases significantly with increasing temperature. Both kinetic and thermodynamic results showed that in the presence of 4DMAP, the forward and reverse reactions are second and first order, respectively. The existence of side reactions, reactivity of two styrene-maleic anhydride copolymers of different MA contents as well as two aliphatic alcohols of different lengths are also addressed. © 1993 John Wiley & Sons, Inc.
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  • 7
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 949-955 
    ISSN: 0887-624X
    Keywords: radical polymerization ; 3-methylene-5,5′-dimethyl-2-pyrrolidinone ; exomethylene cyclic monomers ; kinetics ; monomer reactivity ratios ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 3-Methylene-5,5′-dimethyl-2-pyrrolidinone (α-MDMP), a cyclic analog of N-substituted methacrylamide, was synthesized and polymerized with α,α′-azobis (isobutyronitrile) (AIBN) in solution. Poly(α-MDMP) is only soluble in dimethyl sulfoxide (DMSO) at room temperature. Thermogravimetry of poly(α-MDMP) showed 10% weight loss at 355°C in air and 400°C under nitrogen, respectively. The kinetics of α-MDMP homopolymerization with AIBN was investigated in DMSO. The rate of polymerization (Rp) can be expressed by Rp = k[AIBN]0.49[α-MDMP]1.0 and the overall activation energy has been calculated to be 73.2 kJ/mol. Monomer reactivity ratios in copolymerization of α-MDMP (M2) with methyl methacrylate (M1) are r1 = 0.71 and r2 = 0.71, from which Q and e values of α-MDMP are calculated as 0.75 and -0.43, respectively. © 1993 John Wiley & Sons, Inc.
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  • 8
    Electronic Resource
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 1053-1067 
    ISSN: 0887-624X
    Keywords: free radical polymerization ; kinetics ; dimethacrylate resins ; diffusion ; DSC ; networks ; temperature effects ; homologous series ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The influence of temperature on the photopolymerization kinetics of oligo(methylene) oxide and oligo(ethylene oxide) dimethacrylate series has been investigated by isothermal DSC. The DSC curves showed a rapid rise in rate due to the Trommsdorff effect, and then a slow decline. A shoulder, apparent on many of the DSC curves at low conversions, became more prominent when the cure temperature was lowered. The kinetics were relatively insensitive to the dimethacrylate structure in the early stages of the reaction, but became more dependent as the reaction proceeded. A previously derived mathematical model, which allows for the influence of diffusion on the rate constants, was used to predict the kinetics. The dependence of the maximum rate and conversion on the curing temperature were adequately described by the model. The experimentally observed shoulder on the rate curve was also predicated as was the evolution of the rate/time curves with curing temperature. Similar predictions were found when a nonsteady state version of the model was used. The radiation intensity exponent varied from 0.3 to 0.6 possibly due to chain-length effects and pseudo-first order termination, respectively. The final degree of conversion increased with curing temperature (Tcure) and was correlated with the flexibility of the dimethacrylate. These data were fitted to a theoretical expression relating the final conversion to the resin Tg and to the Tcure. © 1993 John Wiley & Sons, Inc.
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  • 9
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 1147-1151 
    ISSN: 0887-624X
    Keywords: alginates ; polyelectrolytes ; kinetics ; oxidation ; reduction ; permanganate ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of decomposition of [Alg · Mn VIO42-] intermediate complex have been investigated spectrophotometrically at a constant ionic strength of 0.5 mol dm-3. The decomposition reaction was found to be first-order in the intermediate concentration. The results showed that the rate of reaction was base-catalyzed. The kinetic parameters have been evaluated and found to be ΔS
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  • 10
    Electronic Resource
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 1895-1902 
    ISSN: 0887-624X
    Keywords: 4-methylene-4H-1,3-benzodioxin-2-one ; exo-methylene cyclic monomers ; radical polymerization ; kinetics ; monomer reactivity ratios ; chemical amplification ; decarboxylation ; poly[(o-hydroxyphenyl)acetylene] ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 4-Methylene-4H-1,3-benzodioxin-2-one (MBDOON), an α-substituted cyclic styrene derivative, was synthesized and polymerized readily with 2,2′-azobis(isobutyronitrile) (AIBN) as an initiator in solution. The kinetics of the MBDOON homopolymerization with AIBN was investigated in N-methyl-2-pyrrolidone (NMP). The rate of polymerization, Rp, can be expressed by Rp - k[AIBN]0.52[MBDOON]1.1 and the overall activation energy has been calcualted to be 75.7 kJ/mol. Monomer reactivity ratios in copolymerization of MBDOON (M2) with styrene (M1) are r1 = 0.31 and r2 = 3.20, from which Q and e values of MBDOON can be calculated as 3.0 and -0.7, respectively. Ring-substituted MBDOON monomers such as 6-chloro, 6-methyl, and 7-methoxy derivatives were synthesized and polymerized with AIBN. The 6-substituted MBDOON's readily underwent radical polymerization while the 7-methoxy-MBDOON was slower to polymerize. Poly(MBDOON) is predominantly heterotactic. (rr = 35, mr = 46, and mm = 19%). The polymer releases carbon dioxide at about 200°C and is converted with some depolymerization to poly[(o-hydroxyphenyl)acetylene]. The thermolysis temperature is very much affected by the ring substituent. The onset of carbon dioxide liberation was observed at 140°C in the case of the 7-methoxyl derivative while the 6-substituents had a smaller effect on the decarboxylation temperature. © 1993 John Wiley & Sons, Inc.
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  • 11
    Electronic Resource
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 3405-3415 
    ISSN: 0887-624X
    Keywords: maleated thermoplastic elastomer ; maleic anhydride ; graft ; kinetics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Maleation of a thermoplastic elastomer, styrene-[ethylene-butylene]-styrene (SEBS) triblock copolymer, was carried out by a solution grafting reaction with maleic anhydride initiated by dicumyl peroxide. The reaction products from the graft reaction in xylene, commonly chosen as the solvent for maleation graft reactions, were identified using liquid chromatograph (LC), IR, and 13C-NMR. Side products from the graft reaction were identified by the LC analysis and, it was concluded that xylene affected the graft reaction through its active methyl groups. Reaction mechanisms were investigated by performing free radical kinetics analysis. The reaction orders and the apparent rate constant were estimated. It was concluded that a proper choice of the solvent might favor better graft efficiency. © 1993 John Wiley & Sons, Inc.
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  • 12
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 971-977 
    ISSN: 0887-624X
    Keywords: kinetics ; propylene polymerization ; acceleration stage ; superactive catalyst ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of propylene polymerization catalyzed over a superactive and stereospecific catalyst for the initial build-up period was investigated in slurry-phase. The catalyst was prepared from Mg(OEt)2/benzoyl chloride/TiCl4 co-activated with AlEt3 in the absence or presence of external donor. Despite a very fast activation of the prepared catalyst the acceleration stage of polymerization could be identified by the precise estimation of polymerization kinetics for a very short period of time after the commencement of polymerization (ca. 2 min). The initial polymerization rate, (dRp/dt)0 extrapolated to the beginning of the polymerization was second order with respect to monomer concentration. The dependence of initial polymerization rate on the concentration of AlEt3 could be represented by Langmuir adsorption mechanism. The initial rate was maximum at about Al/Ti ratio of 20. The activation energy for the initiation reaction was estimated to be 14.3 kcal/mol for a short-time polymerization. The addition of a small amount of p-ethoxy ethyl benzoate (PEEB) as an external donor increased the percentage of isotactic polymer, which was obtained after 120 s of polymerization, to 98% and the initial polymerization rate decreased sharply as [PEEB]/[AlEt3] increased. © 1994 John Wiley & Sons, Inc.
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  • 13
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1377-1384 
    ISSN: 0887-624X
    Keywords: ozonization ; grafting ; kinetics ; radical polymerization ; EVAg-styrene ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymers can be ozonized with an ozone/oxygen mixture to create peroxides and hydroperoxides on the polymer chain. These heat-sensitive functional groups can be used to initiate radical polymerization of vinyl monomers and give graft copolymers. The properties of these copolymers are well described in literature; however, we notice that available data concerning decomposition rate constants are inconsistent. Decomposition rate measurements, time of assay of free radicals and stability of the ozonized polymers do not give the same results. In this work, we studied the kinetics of the styrene polymerization initiated by an ozonized ethylene vinyl acetate copolymer. Consequently, the f·kd product can be calculated (f is the efficiency and kd the decomposition rate constant). The ozonized copolymer is not similar to usual radical initiators. The initial viscosity of the solution has an important effect on the calculation of the kinetic values. Activation energy and Arrhenius coefficient are different than the one obtained for the usual initiators. © 1994 John Wiley & Sons, Inc.
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  • 14
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1471-1480 
    ISSN: 0887-624X
    Keywords: methyl methacrylate ; redox polymerization ; kinetics ; mechanism ; additives ; iron saccharinate ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The role of N,N-dimethyl-p-toluidine (DMPT) and saccharin as accelerators in the polymerization of methyl methacrylate initiated by the redox decomposition of cumene hydroperoxide (CHP) in the presence of iron saccharinate has been kinetically investigated. DMPT reduces ferric ions to ferrous ions, so that an equilibrium is established between the two oxidation states. With the assumption of a steady-state concentration of propagating radicals, the rate of initiation was deduced from the rate of polymerization and the kinetic orders with respect to each compound involved in the initiation step have been determined. The reaction is first-order in CHP, iron saccharinate, and saccharine and second-order in DMPT. In a proposed scheme, Fe2+ ions, complexed by two DMPT molecules, are much more reactive than uncomplexed Fe2+ and saccharin activates the decomposition of CHP by protonation of the O—O bond. This mechanism, similar to that proposed in the case of copper saccharinate, explains the synergistic effect of both accelerators. © 1994 John Wiley & Sons, Inc.
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  • 15
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1755-1760 
    ISSN: 0887-624X
    Keywords: ring-opening metathesis ; kinetics ; polynorbornene ; living polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Concerning the study on the relation between structural parameters and reactivity in ring-opening metathesis polymerization of cyclo-olefins, the “living” polymerization of norbornene initiated by Schrock's-type complexes was considered as a reference and studied from the kinetic point of view. First kinetic orders with respect to both monomer and active species allow the values of absolute rate constants of propagation to be determined. The thermodynamic parameters obtained from kinetic experiments performed at different temperatures seem to indicate that monomer coordination and metallacycle formation are rate-determining steps in the process studied. © 1994 John Wiley & Sons, Inc.
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  • 16
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 633-642 
    ISSN: 0887-624X
    Keywords: free radicals ; grafting ; kinetics ; methacrylate ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of grafting a basic monomer, 2-(dimethylamino)-ethyl methacrylate (DMAEMA) to hydrocarbon substrates have been investigated. These systems were chosen as models for the grafting of a homopolymerizable monomer to polyolefins such as polyethylene. The reactions with squalane and n-eicosane were initiated by an organic peroxide, 2,5-dimethyl 2,5 dit-butylperoxy)-3-hexyne; grafting yields become significant at high reaction temperatures and low monomer concentrations. In squalane, the order of reaction with respect to monomer increased from about 1.1 for 0.22-0.44M DMAEMA to almost 2 at 0.69M DMAEMA; the order with respect to initiator was 0.56. The overall activation energy in the 130-160°C temperature range was, however, surprisingly low, 42±5 kJ mol-1. When analytical data were used to separate the overall rate into those for grafting and homopolymerization, different kinetic paths were observed for the competing reactions. These results are interpreted in terms of two different mechanisms; intramolecular chain transfer plays an important role in grafting, while depropagation becomes a major factor in homopolymerization at temperatures above 150°C. © 1995 John Wiley & Sons, Inc.
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  • 17
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 673-689 
    ISSN: 0887-624X
    Keywords: epoxy/amine mechanism ; crosslinking ; rate law ; diffusion limit ; kinetics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The bulk phase kinetics of an epoxy (DGEBA) /amine (DDS) thermoset have been studied using DSC, FTIR, and 13C-NMR. In the absence of catalyst, the reaction was found to involve a main exothermic reaction between epoxide and amine hydrogen and a side reaction between tertiary amine formed in the main reaction and epoxide. The main reaction was exothermic while the side reaction had no discernable exotherm. Etherification did not occur to any significant extent. Since only the main reaction is exothermic, DSC was very useful for studying the main reaction kinetics. FTIR was used for determining whether epoxide and amine hydrogen were consumed at different rates as a way of following the side reaction. An IR band previously unused by other investigators was used to monitor the amine hydrogen concentration. NMR confirmed the above mechanism by identifying the formation of a quaternary ammonium ion/alkoxide ion pair as a reaction product of tertiary amine and epoxide. This mechanism has been successfully fit to a rate law valid over the entire extent of reaction. The rate constant for the epoxy/amine addition reaction was found to depend on hydroxide concentration (extent), reaction temperature, and glass transition temperature and included contributions from uncatalyzed and autocatalyzed parts. The side reaction (quaternary ammonium ion formation) formed weak bonds which did not affect the overall system Tg. Both reactions were second order. The rate constants for the main reaction first increase with increasing extent due to autocatalysis by hydroxide before decreasing due to the diffusion limit caused by gelation and vitrification. © 1995 John Wiley & Sons, Inc.
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  • 18
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2533-2549 
    ISSN: 0887-624X
    Keywords: free radical ; grafting ; kinetics ; model ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Graft site initiation occurs by primary radical and/ or polymeric radical attack on the back-bone polymer. The controlling mechanism is determined by the structure of the backbone and the activity of the free radicals. The efficiency of incorporating monomer into the graft chains depends upon the graft site initiation mechanism and the mode of polymer chain termination (recombination or disproportionation). A kinetic analysis results a series of uniquely different expressions describing the graft efficiency, φ corresponding to different combinations of graft site initiation and chain termination mechanisms. The dependency of φ upon monomer, initiator, and backbone concentrations is different from case to case. The complete kinetic model is capable of predicting reaction rate, graft efficiency, graft frequency, graft ratio, and molecular weight averages and distributions. Simulations are provided to compare predicted results with experimental data for two different systems which show contrasting mechanisms of graft site initiation and mode of termination. © 1995 John Wiley & Sons, Inc.
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  • 19
    ISSN: 0887-624X
    Keywords: isobutylene polymerization ; living carbocationic ; conventional carbocationic ; proton trap ; mechanism ; kinetics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of the proton trap, 2,6hyphen;di-tert-butylpyridine (DtBP), on the polymerization of isobutylene (IB) induced by the “HX”/TiCl4 (“HX” = protoic impurity) intiating system has been studied. Significantly, in the presence of a large (∼ 40 molar) excess of DtBP relative to “HX”, free proton-induced chain transfer-dominated conventional IB polymerization is converted to living polymerization. In the absence of the proton trap the kinetics are dominated by rapid proton-induced processs which overwhelm the relatively slower living polymerization. These investigations also led to a quantitative assessment of the concentration of initiating species: [“HX”] = 1.46 × 10-4 mol/L. The polymerizations are first-order in monomer and the apparent rate constants of propagation drop precipituously with increasing DtBP concentration until a constant low value is reached. The rate of formation of propagating living chains has been expressed quantitatively. Chain transfer is bimolecular and first order in monomer, and kinetic investigations led to a quantitative description of the effect of proton trap concentration on the apparent first order chain transfer constant. The results have been explained in terms of a simple mechanistic scheme. © 1996 John Wiley & Sons, Inc.
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  • 20
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 575-585 
    ISSN: 0887-624X
    Keywords: microemulsion copolymerization ; kinetics ; polymer particles ; micelles ; acrylonitrile ; butyl acrylate ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oil-in-water microemulsion copolymerizations of butyl acrylate and acrylonitrile initiated by water (ammonium peroxodisulfate, AP) - and oil (dibenzoyl peroxide, DBP) - soluble radical initiators were investigated. Copolymerizations show two distinct nonstationary rate regions. The maximum rate of polymerization is found to be proportional to the 0.48th and 0.65th power of the AP and DBP concentration, respectively. The rate per particle is found to be proportional to the 0.05th and 0.2nd power of the AP and DBP concentration, respectively. The rate of polymerization decreases with increasing the acrylonitrile concentration. The number of particle increases with increasing conversion up to 50-70%. The number-average molecular weight increases with conversion up to ca. 20% and then decreases. The number-average molecular weights were found to decrease with increasing the concentration of both initiator and acrylonitrile. The experimental results were discussed in terms of the water-phase polymerization, the chain-transfer and radical desorption events, the particle nucleation during the whole polymerization, and recruiting monomer and emulsifier from the free monomer-swollen emulsifier micelles. © 1996 John Wiley & Sons, Inc.
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  • 21
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 3379-3387 
    ISSN: 0887-624X
    Keywords: copolymerization of ethylene and 1-butene ; Cr/silica catalyst ; yields ; kinetics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel slurry reactor was used to investigate the copolymerization behavior of ethylene and 1-butene in the presence of 1 wt % Cr on Davison silica (Phillips-type) catalyst over the temperature range of 0-50°C, space velocity of about 0.0051 [m3 (STP)]/(g of catalyst) h, and a fixed ethylene to 1-butene feed mole ratio of 95 : 5. The effect of varying the ethylene to 1-butene feed ratios, 100 : 0, 96.5 : 3.5, 95 : 5, 93 : 7, 90 : 10, 80 : 20, and 0 : 100 mol/mol at 50°C was also studied. The addition of 1-butene to ethylene typically increased both copolymerization rates and yields relative to ethylene homopolymerization with the same catalyst, reaching a maximum yield for an ethylene: 1-butene feed ratio of 95 : 5 at 50°C. The incorporation of 1-butene within the copolymer in all cases was less than 5 mol %. The average activation energy for the apparent reaction rate constant, ka, based on total comonomer mole fraction in the slurry liquid for the ethylene to 1-butene feed mole ratio of 95 : 5 in the temperature range of 50-30°C measured 54.2 kJ/mol. The behavior for temperatures between 30 to 0°C differed with an activation energy of 98.2 kJ/mol; thus, some diffusion limitation likely influences the copolymerization rates at temperatures above 30°C. A kinetics analysis of the experimental data at 50°C for different ethylene to 1-butene feed ratios gave the values of the reactivity ratios, r1 = 27.3 ± 3.6 and r2 ≅ 0, for ethylene and 1-butene, respectively. © 1996 John Wiley & Sons, Inc.
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  • 22
    ISSN: 0887-624X
    Keywords: bis(p-vinylphenyl) ether ; step-polymerization ; polymer structure ; mechanism ; kinetics ; molecular weight distribution ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A peculiar step-growth (cationic) polymerization of bis(p-vinylphenyl) ether (BVPE) in nonpolar or slightly polar aromatic solvents in the temperature range from 70 to 150°C in the presence of 2.5-5.0 mmol/L of p-toluenesulfonic acid has been studied. Optimum polymerization conditions were found. New linear unsaturated polymers of BVPE with terminal vinyl groups and weight-average molecular weight from 1500 to 10,000 were obtained. The structure and the formation mechanism of these oligomers and polymers were established, and the accompanying side reactions were considered. The rate constants were measured for eight temperatures, and the activation energy was found to be -42 kJ/mol. The optimum polymerization temperature was about 80°C. © 1996 John Wiley & Sons, Inc.
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  • 23
    ISSN: 0887-624X
    Keywords: solution imidization ; kinetics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this work, thermal solution imidization kinetics of two high performance polyimides, prepared from the polycondensation of pyromellitic dianhydride (PMDA) and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) with 4,4′-bis(3-aminophenoxy)diphenylsulfone (DAPDS) were investigated using nonaqueous titration technique with tetramethylammonium hydroxide. Most of the kinetic investigations, found in the literature, are based on the aromatic p-diamines.1,2 In the present work, attention was focused on imidization kinetics with m-substituted aromatic diamines having electron donating (—O—) and electron withdrawing (—SO2—) groups in the same molecule. Kinetic parameters, namely the rate constants, activation energies, entropies and enthalpies of imidization reactions were determined and compared with the literature values. It is reported in literature3 that electron affinities of dianhydrides and ionization potentials of diamines, have strong influence on the reaction rate and activation energies of imidization. Activation energy (Ea) values were found to be 66 and 57 kJ/mol for DAPDS/PMDA and DAPDS/BTDA respectively, and order of reaction was found to be second order. Polyimides DAPDS/PMDA and DAPDS/BTDA, subjected to kinetic investigation, showed glass transition temperatures of 267°C and 241°C, both were found to be thermally stable up to 500°C. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2981-2990, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3341-3347 
    ISSN: 0887-624X
    Keywords: styrene polymerization ; p-chlorostyrene polymerization ; p-methylstyrene polymerization ; living carbocationic ; common ion effect ; kinetics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of common anion producing salt, tetrabutylammonium chloride (n-Bu4NCl), on the livingness and kinetics of styrene (St), p-chlorostyrene (pClSt), and p-methylstyrene (pMeSt) polymerization initiated by the 2-chloro-2,4,4-trimethylpentane (TMPCl)/TiCl4 system has been investigated. Uncontrolled (conventional) carbocationic polymerization of St and p MeSt can be converted to living polymerization by the use of n-Bu4NCl. Under similar conditions the polymerization of p ClSt is living even in the absence of n-Bu4NCl, although the molecular weight distribution (MWD) of the polymer becomes narrower in the presence of this salt. The apparent rates of polymerizations decrease in the presence of n-Bu4NCl in proportion with the concentration of the salt. The rate of living polymerization of p ClSt is noticeably lower than that of St, while that of p MeSt is higher. The apparent rate constants, kpA, of these polymerizations have been determined, and the effects of the electron donating p Me- and electron withdrawing p Cl-substituents relative to the rate of St polymerization have been analyzed. [For part LXI, see J. Si and J. P. Kennedy, Polym. Bull., 33, 651 (1994)]. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3341-3347, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3613-3615 
    ISSN: 0887-624X
    Keywords: anionic polymerization ; kinetics ; mechanism ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 26
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3697-3705 
    ISSN: 0887-624X
    Keywords: carboxyl-terminated polyamide 12 ; dioxazoline ; decanoic acid ; synthesis ; kinetics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High molar mass Polyester Amide was obtained by coupling reaction of Carboxyl-Terminated Polyamide 12 (CTPA) with a dioxazoline (OO). The analysis of the experimental condition effects on the reaction conversion and the structure of the polymer obtained did not show any particular side reaction. A kinetic study comparing the reactivity of the dioxazoline used with CTPA and decanoic acid (DA) as model reactants showed the equireactivity of the two oxazoline functions and of the acid functions of the CTPA and DA. A kinetic model was proposed. The reaction rate at different temperatures and the activation energy were calculated. The evolution of the different reactant concentrations were modeled and compared with experimental data. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3697-3705, 1997
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  • 27
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3735-3743 
    ISSN: 0887-624X
    Keywords: N-vinylimidazole ; maleic anhydride ; spontaneous copolymerization ; charge transfer complex ; kinetics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Maleic anhydride (MAH) and N-vinylimidazole (NVIM) were found to form a charge transfer complex in 1,4-dioxane. The equilibrium constant, K, of the complex and its composition were calculated from the modified Benesi-Hildebrand equation by using UV spectrophotometry. Spontaneous copolymerization of MAH and NVIM has been studied in the range from 20 to 80 mol % MAH in the feed. The effects of the polymerization temperature, monomer feed composition, and total monomer concentration on the initial rate of polymerization were investigated. The values of overall activation energy, Ea, and overall order with respect to total monomer concentration were calculated. Copolymer compositions were found from the elemental analysis data. Reactivity ratios were calculated by the extended Kelen - Tüdos method. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3735-3743, 1997
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  • 28
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1919-1928 
    ISSN: 0887-624X
    Keywords: emulsion polymerization ; vinylidene chloride ; kinetics ; sodium lauryl sulfate ; potassium persulfate ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Emulsion polymerization of vinylidene chloride was carried out at 50°C using sodium lauryl sulfate as emulsifier and potassium persulfate as initiator, respectively. Contrary to the results so far reported, the stirring rate did not affect the progress of the polymerization and such an abnormal kinetic behavior as the rate of polymerization suddenly drops in the course of polymerization was not observed. The number of polymer particles produced was proportional to the 0.7 power of the concentration of emulsifier forming micelles and to the 0.3 power of the initial initiator concentration, respectively, and was independent of the initial monomer concentration. The rate of polymerization was in proportion to the 0.3 power of the concentration of emulsifier forming micelles, to the 0.5 power of the initial initiator concentration, to the 0.2 power of the initial monomer concentration, and to the 0.45 power of the number of polymer particles, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1919-1928, 1998
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  • 29
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    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 635-641 
    ISSN: 0887-624X
    Keywords: aminolysis ; catalysis ; mechanism ; kinetics ; tautomeric compound ; melt ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The aminolysis of poly(styrene-co-methyl acrylate) (SMA) by octadecylamine in solution and in the melt has been reported in Part I. We now have studied the aminolysis of poly(ethylene-co-methyl acrylate) (EMA) with the same amine in the melt and compared the two sets of data in this paper. With EMA, the data confirmed and precised the catalytic mechanism proposed in Part I. The best tautomeric catalysts are the ones which form an eight-atom ring structure with the ester and amine groups. With EMA aminolysis is faster than with SMA because of the steric hindrance of phenyl groups in SMA. But EMA aminolysis remains a rather slow reaction. In a corotating twin-screw extruder the conversion was only around 4% at 220°C with a mean residence time of 150 s. It was also shown that the EMA/octadecylamine/catalyst system, like the SMA system, is homogeneous in the molten state at temperatures around 200°C.
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  • 30
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    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 345-354 
    ISSN: 0887-624X
    Keywords: polyarylate ; acidolysis ; kinetics ; mechanism ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Model reactions were carried out to simulate the acidolysis process for polyarylate synthesis by using p-tert-butylphenyl acetate (ptBuPhOAc) and benzoic acid in diphenyl ether. p-tert-Butylphenol was formed in the reaction mixture and its concentration stayed constant throughout the reaction. Acetic benzoic anhydride and benzoic anhydride were detected by NMR. Based on this experimental evidence, a mechanism for the acidolysis was proposed involving the mixed anhydride. The kinetics of the acidolysis reaction was studied for this model reaction. The overall reaction order is two and the reaction order with respect to each reactant is one. Second-order reaction rate constants were measured at different reaction conditions (200-250°C). The activation energy (Ea), activation enthalpy (ΔH≠), and activation entropy (ΔS≠) were calculated from these data. The thermodynamic parameters of the acidolysis reaction were also measured for the analogous reaction of p-tert-butylphenyl pivalate (ptBuPhOPiv) and benzoic acid. The kinetics of two other elementary reactions involved in the acidolysis reaction were also studied: p-tert-butylphenol with acetic anhydride or benzoic anhydride, and p-tert-butylphenyl pivalate with benzoic acid.
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    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 1961-1968 
    ISSN: 0887-624X
    Keywords: hydrogenation ; liquid carboxylated nitrile rubber ; homogeneous catalyst ; palladium complex ; characterization ; kinetics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Homogeneous catalytic hydrogenation of olefinic bonds in liquid carboxylated nitrile rubber (L-XNBR) has been carried out selectively in the presence of nitrile and carboxyl functionality using a six-membered cyclopalladate complex of 2-benzoyl pyridine as catalyst. The degree of hydrogenation has been calculated from IR and NMR spectroscopic studies. For example, 68% hydrogenation has been obtained for a sample (containing 0.057 carboxyl equivalent/100 g and 26.1% acrylonitrile) under 2.7 MPa hydrogenation pressure, 0.18 mmol/L catalyst, at 333 K for 1 h in acetone solution. The overall extent of hydrogenation depends on the catalyst-to-double-bond ratio. The kinetics of hydrogenation of L-XNBR has been investigated. The reaction exhibits a pseudo-first order dependence on the concentration of the substrate. The rate constant of the reaction is reduced by the increase in carboxyl and nitrile content of the polymer. The effect of temperature on reaction kinetics has also been studied and the activation energy of hydrogenation of L-XNBR is 20.2 kJ/mol. Intrinsic viscosity of the polymer remains unchanged during the reaction. A significant lowering of the glass transition temperature and improvement of thermal stability have been observed on hydrogenation. © 1992 John Wiley & Sons, Inc.
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  • 32
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    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 1879-1886 
    ISSN: 0887-624X
    Keywords: kinetics ; glass temperature ; thermoset curing ; polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A theoretical approach to thermoset cure kinetics based on Arrhenius kinetics and mobility was developed by considering the activation of the reacting group and chain mobility as elementary steps for reaction. This extended kinetic equation was successfully applied to the curing of an epoxy by an amine, the trimerization of a cyanate, and to the polymerization of methyl methacrylate. Full agreement between theory and experimental data was obtained in all cases. The activation energies for chain mobility were exceptionally low (0.3-1 kJ/mol for bisphenol-A-based epoxy and cyanate) which indicates that the structural units must undergo only small-angle rotational oscillations to allow a reaction. A theoretical time-temperature-transformation (TTT) diagram is also presented. © 1993 John Wiley & Sons, Inc.
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  • 33
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    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 2815-2824 
    ISSN: 0887-624X
    Keywords: thermal polymerization ; radical polymerization ; methyl methacrylate ; kinetics ; high temperature ; impurities ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal bulk polymerization of methyl methacrylate (MMA) in a wide range of temperatures has been studied using a dilatometric reactor. It is shown that, irrespective of the care taken to purify the MMA, the evolution of the time-conversion curve can be explained only if we account for the presence of an impurity associated with the monomer acting as a free radical initiator. The activation energy for the decomposition of this impurity has been estimated as 98 kJ/mol. Having accounted for this impurity, the activation energy for the real thermal polymerization of the MMA has been estimated to be 75 kJ/mol. © 1993 John Wiley & Sons, Inc.
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  • 34
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    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1459-1469 
    ISSN: 0887-624X
    Keywords: methyl methacrylate ; redox polymerization ; kinetics ; mechanism ; additives ; copper saccharinate ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetics of methyl methacrylate polymerization initiated by a redox system [cumene hydroperoxide (CHP)/copper saccharinate] were studied in bulk at 20°C in the presence of accelerators such as N,N-dimethyl-p-toluidine (DMPT) and o-benzoic sulphimide (saccharin). Assuming a steady-state concentration of propagating radicals, the polymerization rate depends on the square root of the initiation rate and the kinetic orders with respect to each compound in the initiation step may be deduced. Initiation is first-order in CHP, copper saccharinate, and saccharin and second-order in DMPT. A reaction scheme consistent with these orders is proposed. The main features are the following: (1) CHP reduces rapidly Cu(II) to Cu(I); (2) a small fraction of Cu(I) is complexed with DMPT; (3) the complexed ions (Cu+, DMPT2) are strong reductants with respect to CHP whereas uncomplexed Cu+ are almost inactive; (4) the decomposition of CHP is strongly catalyzed by saccharin (protonated CHP is 13000 times more reactive than free CHP). Thus both accelerators are necessary to get high polymerization rates. © 1994 John Wiley & Sons, Inc.
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  • 35
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 175-184 
    ISSN: 0887-624X
    Keywords: epoxy-amine ; methacrylate ; acrylate ; prepolymers ; synthesis ; kinetics ; Michael reaction ; catalyst ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Epoxy-amine methacrylated prepolymers are prepared in a 1-step synthesis by the reaction of Bisphenol A diglycidyl ether, glycidyl methacrylate, and different diamines. The adaptation of these reactions to production processes with a reduced reaction time requires a kinetic control and the use of efficient catalysts. The comparative kinetic treatment of the epoxy-amine reaction in the frame of Horie's and Rozenberg's kinetic schemes have been made. Cases where an efficient acid catalyst is used are also examined. Structural studies of these reactions established the occurrence of a Michael amine/double bond addition, when some amines are used. © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 1537-1543 
    ISSN: 0887-624X
    Keywords: 2,5-dimethylene-2,5-dihydrofuran ; kinetics ; copolymerization ; polymeriza-bility ; highly conjugative ; electron-donating ; new monomer ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Spontaneous homopolymerization of 2,5-dimethylene-2,5-dihydrofuran (DDF) was studied. The polymerization rates in two different initial monomer concentrations of DDF were analyzed with the first-order and second-order kinetics, and the homopolymerization of DDF was found to obey the first-order kinetics. The Arrhenius plot of the apparent rate constants at 30, 40, 50, and 60° gave an overall activation energy of 68.0 kJ/mol for the polymerization of DDF. From the comparison of the apparent rate constants at -78° and the time (the so-called half-life time) to decrease in half the monomer concentration for DDF with the corresponding values for p-xylylene (QM), DDF was found to be a less reactive monomer than QM. The copolymerizations of DDF with vinyl monomers such as acrylonitrile (AN), α-chloroacrylonitrile (CIAN), diethyl fumarate (DEF), and fumaronitrile (FN) were carried out in chloroform at 50° in the presence of AIBN to obtain the monomer reactivity ratios r1(DDF) = 30.0 ± 3.0 and r2 (AN) = 0 for the DDF-AN system, r1 (DDF) = 1.55 ± 0.2 and r2(CIAN) = 0 for the DDF-CIAN system, r1(DDF) = 3.88 ± 0.2 and r2(DEF) = 0 for the DDF-DEF system, and r1(DDF) = 2.41 ± 0.1 and r2 (FN) = 0 for the DDF-FN system, respectively. As the monomer reactivity ratios of r2 for all systems were zero, Q and e values of DDF were calculated from the combination of two r1 (DDF) values of any two copolymerization systems to be the 7.64 to 6.63 ×1021 range for Q and the -0.70 to -6.31 range for e, indicating that DDF is a highly conjugative and electron-donating monomer. © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 1573-1580 
    ISSN: 0887-624X
    Keywords: polyurethanes ; solution polymerization ; naphtalene diisocyanate ; kinetics ; NMR spectroscopy ; size exclusion chromatography ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction between polycaprolactone and 1,5-naphtalene diisocyanate has been investigated in solvents with different dielectric constants and hydrogen bonding powers (toluene, ethyl acetate, ethyl methyl ketone), and in the same solvents with the addition of a catalytic amount of dimethyl sulfoxide (DMSO). The reaction was considered to proceed over two steps, the reaction of the first NCO group being faster. The course of the reaction was measured by titration of the unreacted NCO groups, 1H- and 13C-NMR spectroscopy, and size exclusion chromatography. By titration only the overall reaction order and reaction rate constants could be determined. DMSO accelerated the reaction in all three solvents, which was explained by the stabilization of the activation complex by DMSO. Both steps of the reaction could be specified by NMR spectroscopy. The ratio between the reaction rate constants for the first and the second step decreased with the increased hydrogen bonding strength of the solvent and with DMSO. By SEC only the reaction of the first NCO group could be determined due to the low resolution for higher molar mass reaction products with a broad distribution. The values obtained for the first step reaction rate constants were in good agreement with NMR values. © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 1119-1124 
    ISSN: 0887-624X
    Keywords: poly(vinyl alcohol) ; silylation ; hexamethyldisilazane ; liquid ammonia ; kinetics ; properties ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Silylation of poly(vinyl alcohol) has been performed with hexamethyldisilazane in liquid ammonia in an autoclave. This novel procedure has the advantage that the educt, the reagent, and the product are soluble in ammonia, which works under homogeneous conditions. No salt like by-products are formed and no tedious purification of the product is necessary. The degree of silylation has been adjusted through the ratio of silylating agent to hydroxy groups. Random incorporation of trimethylsilyl groups was proven by the linear dependence of the glass transition temperature from the degree of silylation and the solubility of the partially silylated material. Quantitative investigation of the silylation reaction showed first-order kinetics for the initial and final stages of the reaction indicative of a reaction where k1 〉 k2 〉 k3. © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 1209-1217 
    ISSN: 0887-624X
    Keywords: polyethylene ; functionalization ; transesterification ; surface ; fluorescence ; kinetics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of solvent on the accessibility and reactivity of an ester-bound fluorophore at a functionalized polyethylene-solvent interface have been studied. Fluorophore-labeled polyethylene surfaces were prepared by blending together a small amount of a pyrene esterterminated ethylene oligomer and a host linear low density polyethylene in solution. Films cast from such solutions were then studied by fluorescence spectroscopy to show that a significant number of the entrapped pyrene groups were at the polyethylene-solvent interface and capable of reaction with soluble reagents. Subsequently, transesterification of these ester-bound pyrenes using various sodium alkoxides in alcohol, alcohol-toluene, or alcohol-tetrahydrofuran solvent mixtures was studied by fluorescence and UV-visible spectroscopic analysis of the supernatant. The extent of alcoholysis of such esters was found to be significantly affected by the solvent chosen and by the structure of the alcohol. © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 3427-3430 
    ISSN: 0887-624X
    Keywords: photopolymerization ; methyl methacrylate ; methylaluminoxane ; kinetics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1873-1889 
    ISSN: 0887-624X
    Keywords: free-radical polymerization ; kinetics ; hydrogel ; thermoset ; crosslinking ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An experimental study was carried out to investigate the effect of ethylene glycol dimethacrylate (EGDMA, as a crosslinking agent) content on the curing kinetics of the polymerization of 2-hydroxyethyl methacrylate (HEMA), using differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). EGDMA may cause a crosslinking-facilitated gel effect which reduces the termination rate of living free radicals and enhances the overall reaction rate, but it may also induce a diffusional resistance for the reactants so that some free monomers are trapped and pendant vinyl groups are prohibited from reaction by the crosslinked structure. At higher content of EGDMA, the later effect becomes predominant, and the reaction rate and the final conversion are limited. The exothermic peak of the curing reaction tends to carry a shoulder and then split into two peaks as the amount of EGDMA is increased, possibly due to a later reaction of the trapped monomers and pendant vinyls. The heat of reaction measured by DSC in the scanning mode is 61.2 kJ/mol C=C. The activation energy (E) of the curing reaction ranges from 56.5 to 78.3 kJ/mol C=C depending on the EGDMA content and the type of operation. The diffusion-limited reaction rate and the different thermal history experienced in the nonisothermal and isothermal curing can result in variations of the results in the activation energy measurement. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1873-1889, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2075-2096 
    ISSN: 0887-624X
    Keywords: heterogeneous Ziegler-Natta catalyst ; diffusion limitation ; kinetics ; temperature perturbation ; gas phase ; particle growth ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Monomer transport and polymerization kinetics are two key phenomena in olefin polymerization with heterogeneous transition metal catalysts. To have a better understanding of these interrelated kinetics and diffusion phenomena, a quantitative calculation of the monomer diffusion directly from experimental study is essential. In this work, a novel temperature-perturbation technique is developed to systematically study the kinetic and diffusion limitations in catalyzed gas phase olefin polymerization. A physical model of the particle growth mechanism as well as its mathematical representation is presented and the diffusion limitations occurring in the system at high temperature are characterized and quantitatively analyzed. Finally, the practical implications of the results of this study on the operation of industrial scale polyolefin reactors are examined. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2075-2096, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2689-2695 
    ISSN: 0887-624X
    Keywords: kinetics ; mechanism ; emulsion copolymerization ; acrylamide ; styrene ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The seeded emulsion copolymerizations of styrene and acrylamide were carried out at 50°C using polystyrene latex particles as the seed and potassium persulfate as the initiator, respectively. It was found that the change in the number of seed particles initially charged causes a drastic change in the kinetic behavior of this seeded emulsion copolymerization system: when the number of seed particles initially charged was less than a certain critical value, both styrene and acrylamide started polymerization from the beginning of the reaction. However, when the number of seed particles was higher than this critical value, an apparent induction period suddenly emerged only for acrylamide polymerization, that is, acrylamide did not start polymerization until the styrene conversion exceeded around 75%, while the styrene polymerization started and continued very smoothly from the beginning of the reaction. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2689-2695, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 3073-3080 
    ISSN: 0887-624X
    Keywords: direct esterification ; BHET ; EG ; DEG ; OH reactivity ; kinetics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: For revealing diethylene glycol (DEG) formation in poly(ethylene terephthalate) (PET) synthesis, this research focused on finding the stage most critical for DEG formation. It is found that the esterification stage was the most critical stage for DEG formation during production of PET through the direct esterification process. In addition, the kinetics of the formation of DEG (ether bond), which is mainly produced from hydroxyl end groups of ethylene glycol (EG) and bis-hydroxyethyl terephthalate (BHET) oligomer, was investigated. The results show that the reactivity of BHET-OH functional group is greater than that of EG-OH functional group in the reaction to produce ether bonds. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3073-3080, 1998
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    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 1083-1088 
    ISSN: 0887-624X
    Keywords: tetrafluoroethylene ; propylene ; bulk copolymerization ; kinetics ; properties ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bulk copolymerization of tetrafluoroethylene (TFE) with propylene (P) initiated by tert-butyl peroxybenzoate (TBPB) in the temperature interval 323-363 K, monomer pressure from 2 to 9 MPa, and TFE and P molar ratio from 20/80 to 90/10 was carried out. The effect of these reaction conditions on the yield, molecular weight, and polymer composition of the copolymer synthesized was studied. Rubber-like alternating copolymers in a wide range of monomer compositions of TFE and P (from 40 to 80 mol %) were obtained. The reaction proceeds in a stationary state without an induction period. Monomolecular chain transfer reaction (Cp = 5 × 10-4) to propylene takes place. The relative reactivity ratio of P and TFE (0.15 and 0.01, respectively) and apparent activation energy Eα = 75.8 kJ/mol of the reaction were determined.
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    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 471-484 
    ISSN: 0887-624X
    Keywords: hydrogenation ; nitrile rubber ; rubber ; palladium acetate catalyst ; modification of rubber ; kinetics ; characterization of rubber ; spectroscopic analysis ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hydrogenated nitrile rubber was prepared by using palladium acetate as the homogeneous catalyst system. The effect of different reaction parameters on the level of hydrogenation was studied. The extent of hydrogenation increased with increase in reaction time, temperature, pressure, and catalyst concentration. A maximum conversion of 96% could be achieved. The degree of hydrogenation was estimated from IR and NMR spectroscopy. The selectivity of the catalyst in reducing —C=C— in presence of —C≡N was supported by IR and 13C-NMR spectra. ESCA studies further confirmed this observation. Properties of hydrogenated nitrile rubber were investigated by various techniques such as gel permeation chromatography (GPC), glass transition temperature (Tg), stress-strain behavior and rheological measurements. GPC studies showed no significant change in molecular weights of the products after the reaction. Tg value decreased with an increase in the level of hydrogenation. The ultimate stress improved significantly with the increase in the extent of hydrogenation. The die swell decreased with hydrogenation at a particular shear rate. The kinetics of the NBR hydrogenation were investigated. With the increase of the hydrogen pressure and catalyst concentration, the rate of the reaction increased. The reaction was apparently first order with respect to olefinic substrate at higher hydrogen pressure. The apparent activation energy, enthalpy, and entropy of the reaction were calculated as 29.9 kJ/mol, 27.42 kJ/mol, and -0.20 kJ mol-1 K-1, respectively.
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    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 625-634 
    ISSN: 0887-624X
    Keywords: catalysis ; mechanism ; kinetics ; aminolysis ; tautomer ; molten state ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The aminolysis of poly(styrene-co-methyl acrylate) (SMA) by octadecylamine was studied in solution and in the melt at temperatures around 200°C. This reaction is rather slow, so several types of catalysts were tested to accelerate it. The most efficient is 2-pyridone, a compound in tautomeric equilibrium with 2-hydroxypyridine. A mechanism of the catalytic reaction is proposed whereby the tautomeric nature of the catalyst plays a key role in a very important step of the reaction, namely the proton transfer. This mechanism is confirmed by the kinetic data determined in a 1,2,4-trichlorobenzene solution and in the melt. In addition, it was found that the kinetic data obtained in both media are very close, indicating no significant difference of local polarity in the two reaction media. Data also show only a minor effect due to difference in viscosity. Finally, the question of the homogeneity of the molten medium is discussed.
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    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 2389-2397 
    ISSN: 0887-624X
    Keywords: polymethacrylic acid ; thermal degradation ; kinetics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal degradation of polymethacrylic acid was found to have two separate decomposition regions. The first decomposition region, due to anhydride formation primarily, was caused by the conversion of polymethacrylic acid to polymethacrylic anhydride. This reaction followed first-order kinetics and had an activation energy of 40.5 kcal/mol. The second decomposition region was the thermal degradation for the corresponding polymethacrylic anhydride. In this region, the fragmentation of anhydride rings structure in polymethacrylic anhydride constitutes the major decomposition reaction with an activation energy of 37.4 kcal/mol. © 1992 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 403-426 
    ISSN: 0887-624X
    Keywords: emulsion polymerization ; ethylene-vinyl acetate ; semi-batch emulsion ; copolymerization ; kinetics ; reactor design ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ethylene-vinyl acetate emulsion copolymers are useful materials for paint, adhesive, and coating applications. The kinetics of their production remain largely unstudied, probably due to the inherent difficulties associated with pressure polymerizations. Polymerizations at elevated pressures are in general more difficult to understand and control, and relatively more expensive since one has to consider the added cost of increased safety precautions. Reported here are the preliminary results of an extensive experimental investigation of the variables which govern the ethylene-vinyl acetate emulsion process. Two redox initiator systems have been identified as more suitable for the polymerization process. Two buffer systems, namely sodium acetate/acetic acid and potassium phosphate, have been used to effectively control pH. The addition of n-hexane has offered an effective method of enhancing the ethylene content in the copolymer produced. Several other important variables including agitation/mixing and emulsifier type and concentration have been identified and are discussed. These screening experimental observations have aided in the selection of suitable design levels for future, more focused experimentation to quantify the effects of reaction variables on the latex and copolymer properties of interest. A review of the existing literature on ethylene-vinyl acetate copolymer properties and processes is also included. © 1993 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 45-50 
    ISSN: 0887-624X
    Keywords: free radical polymerization ; dimethylphenyl methacrylates ; kinetics ; dilatometry ; dipoles interaction ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of free radical polymerization of all six existing isomeric dimethylphenyl methacrylates were studied in bulk at 60°C, initiated by dilauroyl peroxide, using dilatometry. The different polymerization rates observed, resulting from the different monomer structures, are discussed in terms of steric and other effects, considering also the previous results for tolyl methacrylates. © 1993 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 505-514 
    ISSN: 0887-624X
    Keywords: polylactide ; end-functionalization ; living polymerization ; kinetics ; mechanism ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Functional aluminum alkoxides, such as Et3-pAl(O—CH2—X)p, where p = 1,3 and X = a functional group, are very effective initiators for the (D, L)-lactide polymerization in toluene at 70°C. The coordination-insertion type of polymerization is living. Linear polyesters of a predictable molecular weight and a narrow molecular weight distribution are obtained within the period of time required for the total monomer conversion. The functional group (X) associated with the active alkoxy group of the initiator is selectively and quantitatively attached to one chain end, whereas the second end group is systematically a hydroxyl function resulting from the hydrolysis of the living growing site. Asymmetric telechelic polylactides are thus obtained in a perfectly controlled way. A kinetic study has shown that the polymerization is first order in both the monomer and initiator. © 1993 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 1105-1109 
    ISSN: 0887-624X
    Keywords: electropolymerization ; m-aminophenol ; kinetics ; rotating disc voltametry ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics and mechanism of electropolymerization of m-aminophenol (mAP) has been investigated in acetonitrile (AN) and methanol (MeOH) media. The rate of polymerization is found to be proportional to [mAP] (current)0.5 at moderate current densities; at higher current densities, the rate of polymerization is independent of current density. A suitable mechanism has been proposed and the rate equation is derived to explain the observed factors. Rotating disc voltametry revealed that at low current densities, the rate of polymerization is charge controlled, while at high current densities it is diffusion controlled. The physicochemical characteristics of AN make it a better solvent than MeOH. © 1993 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 1449-1452 
    ISSN: 0887-624X
    Keywords: polymerization, gel-free ; MBA ; PDP-MSA ; TGA ; kinetics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Gel-free cyclopolymerization of N,N′-methylenebisacrylamide has been carried out using potassium peroxodiphosphate (PDP) as initiator in combination with different activators such as mercaptosuccinic acid (MSA) and thioglycollic acid (TGA) in an inert atmosphere at 45 ± 1°C and 40 ± 1°C, respectively. The rate of polymerization was found proportional to the first power of the monomer and activator concentration and the half-power of PDP in both redox systems. A mechanism involving cyclopolymerization in the propagation path has been proposed. © 1993 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 3387-3396 
    ISSN: 0887-624X
    Keywords: block copolymers ; free radical polymerization ; polydimethylsiloxane ; kinetics ; synthesis ; thiuram disulfide ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: PDMS-based macrothiuram disulfides of different molecular weights capable of being used as macro-thermal iniferters towards deriving PDMS-containing triblock copolymers were synthesized and characterized. The synthesis of ω-(secondary amine)-terminated PDMS were accomplished by the hydrosilylation reaction of silyl hydride terminated PDMS with allyl-N-methylamine. Macroamines were eventually transformed to macroiniferters by the thiocarbamylation reaction and oxidative coupling. Kinetics of polymerization studied in the case of MMA and styrene in bulk, and as in toluene solution in case of MMA, revealed that the macroiniferters are as efficient as their microanalogues from the point of view of their initiating and chain-terminating properties. The different kinetic parameters were determined and discussed. © 1993 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 2839-2854 
    ISSN: 0887-624X
    Keywords: polyamic acid models ; kinetics ; mechanisms ; RMN solid-state rayons X ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have synthesized and studied the ring dehydration mechanisms and kinetics of polyamic acid models in solution and in the solid state using 13C-NMR (solid and liquid), HPLC, FTIR, and x-ray diffraction. Results obtained in solution show the role of temperature, catalysts, and the basicity of the amine in ring dehydration mechanisms and kinetics, as well as conformation and intramolecular bonds in the amic acid bond in the solid state. © 1993 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 539-555 
    ISSN: 0887-624X
    Keywords: emulsion polymerization ; semi-batch emulsion ; copolymerization ; kinetics ; process optimization ; factorial experiments ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The application of factorial experiments to optimize the ethylene-vinyl acetate emulsion polymerization process is described herein. A prior extensive experimental phase identified those variables that are most important for ethylene-vinyl acetate emulsion copolymer production. The effects of temperature, pressure, added co-solvent, vinyl acetate feed rate and emulsifier type, and concentration on the rate of polymerization, cumulative copolymer composition, molecular weight averages, and particle size and number are described in this article. The primary objectives of this research were to increase the amount of ethylene that could be incorporated into the copolymer at reduced temperatures and pressures (our target was a copolymer with an ethylene content of 30% by weight at 500 psig and 20°C versus the commonly employed industrial conditions in excess of 1000 psig), to achieve an improved process understanding, and to accumulate reliable data for modelling purposes. A copolymer containing 34% by weight of ethylene has been achieved at a pressure of 500 psig and a temperature of 20°C. The confusion present in the literature surrounding emulsifier effects has also been clarified. A discussion of hydrolysis, experimental reproducibility, and glass transition temperatures is also included. The sequential nature of the experimental process is illustrated throughout these optimizing experiments. © 1994 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 3453-3464 
    ISSN: 0887-624X
    Keywords: quaternization ; poly(vinylpyridines) ; alkyl halide ; kinetics ; steric hindrance ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Quaternization reactions of poly(vinylpyridines) with alkyl halides show retardation in excess of that predicted by the classical second-order kinetics. Based on the classical collision and transition state theories, a kinetic model has been developed to quantify such retardation, in which the overall reaction rate is characterized by a rate constant k0 of the intrinsic reactivity between a pyridyl group and an alkyl halide group, and by a steric hindrance effect parameter α. The latter accounts for the degree to which the rate of collisions of reactants is reduced, or to which the freedom of movement of the reactants in the transition state is restricted as the reaction proceeds. The resulting kinetic expression has been validated using experimental results reported in the literature and those of our own. The functional dependence of k0 and α values on the nature of poly(vinylpyridines) and that of alkyl halides is explained. Other factors affecting k0 and α, including changes in macromolecular dimensions and/or in the distribution of residue environment, quality of solvent, and reaction temperature, are discussed. © 1993 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1761-1778 
    ISSN: 0887-624X
    Keywords: emulsion terpolymerization ; high solids content ; kinetics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the high solids content emulsion terpolymerization of vinyl acetate, methyl methacrylate, and butyl acrylate were investigated. The effect of feed flow rate, total amount of emulsifier, distribution of emulsifier between the initial charge and the feed, concentration of initiator, and solids content on the time evolution of the conversion, terpolymer composition, and total number of polymer particles were investigated. The experimental results were analyzed by means of a mathematical model that incorporated the main features of the system. © 1994 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1447-1458 
    ISSN: 0887-624X
    Keywords: epoxide ; cationic polymerization ; kinetics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cationic nonlinear polymerization of diglycidyl ether of Bisphenol A (DGEBA) in the presence of a diluent γ-butyrolactone (BL) was initiated by the BF3-4-methoxyaniline (MA) complex. The reaction was studied by size exclusion chromatography, DSC, and dynamic mechanical analysis. Reaction mechanism involves a fast formation of adducts of DGEBA with MA released from the initiator. Formation of spiro orthoesters (S) by reaction of BL with DGEBA and homopolymerization of DGEBA as well as copolymerization with S follow. Gelation occurs at 60°C within a few minutes at conversion of epoxy groups (ξE)c = 0.20-0.45. The networks cured under optimum conditions show high glass transition temperature, Tα = 178°C. The mechanism-structure-property relations are discussed. © 1994 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 237-248 
    ISSN: 0887-624X
    Keywords: styrene ; ethyl acrylate ; reactivity ratios ; kinetics ; copolymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An experimental study of the bulk-free radical copolymerization of styrene (STY)/ethyl acrylate (EA) initiated by 2,2′-azobisisobutyronitrile was conducted. Reactivity ratios were evaluated using both nonlinear least-squares (NLLS) and error-in-variables model (EVM) techniques. A thorough study of the kinetics over the full conversion range was subsequently carried out at a variety of feed compositions, initiator concentrations, and temperatures, with and without added chain transfer agent (CTA). © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 461-473 
    ISSN: 0887-624X
    Keywords: calorimetry ; styrene ; kinetics ; emulsion polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An automated reaction calorimeter was used to directly monitor the rate of emulsion polymerization of styrene using different emulsifier (sodium lauryl sulfate) and initiator (potassium persulfate) concentrations. By using this technique in conjunction with off-line measurements of the evolution of the particle size distributions, important details of the process were observed. The classical constant rate period (Interval II) often reported for the batch emulsion polymerization of styrene was not seen in this work. Instead, the experimental results suggest that the end of nucleation and the disappearance of monomer droplets take place at approximately the same conversion (36-40%). From the polymerization rate data, important parameters such as the monomer concentration in the polymer particles and the average number of radicals per particle were calculated. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1807-1813 
    ISSN: 0887-624X
    Keywords: ε-caprolactone ; diethylaluminum ethoxide ; anionic coordination polymerization ; kinetics ; aggregation of active species ; solvent effect ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetics of ε-caprolactone (εCL) polymerization initiated with diethylaluminum ethoxide in benzene (C6H6) and acetonitrile (CH3CN) as solvents was studied and compared with the previously studied polymerization conducted in tetrahydrofuran (THF) solvent. Kinetic data were analyzed in terms of the kinetic scheme: “propagation with aggregation,” assuming that actually propagating active species (Pn*) aggregate reversibly into the unreactive (dormant) species $(P^*_n)_m {\buildrel {K_{da}}\over{\rightleftharpoons}} m P^{*}_{n}, P^{*}_{n}+\epsilon CL {\buildrel {k_{p}}\over{\rightarrow}} P^{*}_{n+1}$. The determined equilibrium constants of deaggregation (Kda) decrease with decreasing solvent polarity, namely Kda (in mol2·L-2) = (1.3 ± 0.7)·10-2 (CH3CN), (1.8 ± 0.5)·10-5 (THF), (4.1 ± 0.7)·10-6(C6H6), whereas for the rate constants of propagation the opposite is true, kp (in mol-1·L·s-1) = (7.5 ± 0.3)·10-3 (CH3CN), (3.87 ± 0.01)·10-2 (THF), (8.6 ± 0.9)·10-2 (C6H6) (25°C). The latter effect is explained by a specific solvation (the stronger the higher solvent polarity) of the active species already in the ground state in the elementary reaction of the poly(εCL) chain growth: C2H5[OC(O)(CH2)5]nO(SINGLE BOND)Al(C2H5)2 + εCL → C2H5[OC(O)(CH2)5]n+1O(SINGLE BOND)Al(C2H5)2. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 2955-2966 
    ISSN: 0887-624X
    Keywords: cyanate esters ; spectroscopies ; kinetics ; catalysts ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanisms and kinetics of polymerization of mono- and difunctional cyanate esters are investigated using chromatographic (HPLC) and spectroscopic methods (UV, liquid and solid-state NMR, and FTIR). The results obtained after chromatographic separation and identification of the chemical species present in the reaction medium have enabled us to propose a reaction path and a kinetic model for these thermally polymerized systems. Finally, the polymerization of cyanate ester was studied in the presence of different catalysts (imidazole, AcAcCu and AcAcCr) added directly, without solvent, and showed their influence on mechanisms. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 851-860 
    ISSN: 0887-624X
    Keywords: polyvinyl chloride ; peroxide modification ; crosslinking ; degradation ; electron spin resonance ; kinetics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Peroxide induced crosslinking and degradation of polyvinyl chloride (PVC) were experimentally investigated using an on-line electron spin resonance (ESR) spectroscopy technique. The reaction variables included temperature, peroxide type and concentration. A single line ESR spectrum was observed with its peak-to-peak width decreasing during the reaction. The mechanism involved in the reaction was elucidated based on the radical information. The radical concentration versus reaction time profile exhibited two distinct regions: the chemically initiated reaction continued by the thermal initiation. The addition of peroxide induced and significantly enhanced the thermal initiated crosslinking and degradation. The radical concentration data coupled with the extent of dehydrochlorination gave an estimate of the rate constant of polyene propagation. A significant decrease of the rate constant was observed during the reaction. The gel content and swelling ratio were also measured to provide additional information to the reaction process. The initial gelation rate increased with the increase of temperature and/or peroxide concentration. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 851-860, 1998
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3813-3825 
    ISSN: 0887-624X
    Keywords: reaction calorimetry ; emulsion polymerization ; kinetics ; styrene ; nonionic surfactant ; Triton X-405 ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The emulsion polymerization of styrene was studied using the nonionic surfactant Triton X-405 (octylphenoxy polyethoxy ethanol). Two separate nucleation periods were noted in these polymerizations resulting in bimodal final latex particle size distributions. The partitioning of the surfactant between the phases was found to play the major role in determining the nucleation mechanism(s) in these polymerizations. Although the total concentration of the emulsifier was always added at a level above its critical micelle concentration (CMC) based on the water phase in the recipe, it was found that the portion of the surfactant initially present in the aqueous phase was below its CMC due to the partitioning. This CMC was also found to increase with increasing total surfactant because the distribution of the surfactant (varying ethylene oxide chain length) depended on the partitioning between the phases. Under these conditions, the first of the two nucleation periods was attributed to homogeneous nucleation, while the second was attributed to micellar nucleation. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3813-3825, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 3081-3087 
    ISSN: 0887-624X
    Keywords: TPA ; mol ratio ; DEG ; kinetics ; protons ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This research focused on studies of the effect of terephthalic acid (TPA) addition at the initial feed on diethylene glycol formation (DEG) in the process of polyethylene terephthalate (PET) preparation. Experimental results show that, when the mol ratio of ethylene glycol (EG) with TPA ranges from 1.0 to 1.3, the greater the amount of TPA added at the initial feed, the more DEG formed, and the greater the suppression of the rate of esterification and polymerization. In addition, the kinetics of EG with protons in the etherification reaction was considered in the study. It is found that, during the etherification reaction, the reactivity of hydroxyl end groups with ether bonds is higher than that of hydroxyl end groups on their own, and the activation energy of EG with protons is much lower than that of pure EG on its own. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3081-3087, 1998
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 461-470 
    ISSN: 0887-624X
    Keywords: kinetics ; polyimides ; thermal cure ; infrared spectroscopy ; DSC ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetic mechanism of the thermal cure of a phenylethynyl-terminated imide model compound, 3,4′-bis[(4-phenylethynyl)phthalimido]diphenyl ether (PEPA-3,4′-ODA) and a phenylethynyl-terminated imide oligomer PETI-5 (MW 5000 g/mol) was studied. FTIR was used to follow the cure of the model compound, while thermal analyses (DSC) was used to follow the cure of the PETI-5 oligomer. The changes in IR absorbance of phenylethynyl triple bonds at 2214 cm-1 of PEPA-3,4′-ODA as a function of cure time were detected at 318, 336, 355, and 373°C, respectively. The changes in the glass transition temperature, Tg, of PETI-5 as a function of time were measured at 350, 360, 370, 380, and 390°C, respectively. The DiBenedetto equation was applied to define the relative extent of cure, x, of the PETI-5 oligomer by Tg. For the model compound, the reaction followed first order kinetics, yielding an activation energy of 40.7 kcal/mol as determined by infrared spectroscopy. For PETI-5, the reaction followed 1.5th order, yielding an activation energy of 33.8 kcal/mol for the whole cure reaction, as determined by Tg using the DiBenedetto method. However, the cure process of PETI-5 just below 90% by this method followed first-order kinetics yielding an activation energy of 37.2 kcal/mol. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 461-470, 1998
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    Cell Motility and the Cytoskeleton 13 (1989), S. 239-244 
    ISSN: 0886-1544
    Keywords: sperm ; nucleotide analog ; kinetics ; Stronglyocentrotus purpuratus ; reactivation ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: The 2-substituted ATP analog 2-Chloro ATP was tested for its capacity to support axonemal movement. The movement of sea urchin axonemes reactivated with 2-CI ATP appeared very similar to that with ATP. Detailed waveform analysis indicated that bend angle and shear amplitude were not significantly different for ATP and 2-CI ATP. Although wavelength differs at particular nucleotide concentrations, if normalized to the beat frequency, it is similar for ATP and 2-CI ATP. The main difference in the movement with the two analogs was seen in beat frequency and sliding velocity. The Vmax for beat frequency and mean sliding velocity was lower for 2-CI ATP. The apparent Km for beat frequency and sliding velocity was much lower for 2-CI ATP. The ratio of these two effects, that is, (Vmax/Km) is higher for 2-CI ATP. Thus 2-CI ATP is a good substrate for axonemal movement. The significantly lower Km of 2-CI ATP was also demonstrated by its ability to support oscillatory motion at concentrations below that for ATP. The observations identify the structures and conformation of substrate necessary to support axonemal movement.
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    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 1017-1026 
    ISSN: 0887-624X
    Keywords: kinetics ; metallocene-methylaluminoxane catalyst ; FTIR-ATR spectroscopy ; catalyst deactivation mechanism ; polyoctene ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetic parameters have been measured for octene-1 solution polymerization at 120°C catalyzed by zirconocene with the cocatalyst methylaluminoxane. The polymerizations were performed in an attenuated total reflectance (ATR) reaction cell. The progress of the reactions were followed by observing the disappearance of octene-1 using the 910 cm-1 band measured by FT-IR spectroscopy. The dependence of the reaction rate, Rp, on catalyst concentration and cocatalyst/catalyst ratio was examined. The catalyst deactivation mechanism was studied by fitting the experimental data to mathematical models involving second-order propagation and either first or second order catalyst deactivation. Second-order catalyst deactivation provided a much better fit. The calculated deactivation rate constant, kd, is 21 (Ms)-1. This model is used to determine the propagation rate constant for Al/Zr = 4 × 103 as kp = 19.9 (M s)-1. A decrease in Al/Zr = 3 × 102 lowered the propagation rate constant, kp, to 9.6 (M s)-1 indicating that less than 50% of the initial Zr is active at this Al/Zr ratio.
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    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 797-802 
    ISSN: 0887-624X
    Keywords: selective polymerization ; 4-Vinyl-1-cyclohexene ; Ziegler-Natta catalyst ; isomerization ; kinetics ; copolymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of 4-vinyl-1-cyclohexene (4VCHE) with Ziegler-Natta catalysts was studied. The polymerization of 4VCHE by the vinyl group took place with TiCl3-aluminum alkyls catalysts, while vinylene group of 4VCHE did not participate in the reaction, but it affected the polymerization rate of 4VCHE. The effects of aluminum alkyl and type of TiCl3 on the polymerization were examined. The overall activation energy for the polymerization was estimated to be 41.9kJ/mol. Monomer-isomerization copolymerization of 4VCHE and trans-2-butene occurred with the TiCl3-(i-C4H9)3Al catalyst to give copolymers consisting of 4VCHE and 1-butene units.
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    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 913-928 
    ISSN: 0887-624X
    Keywords: kinetics ; polymerization ; photoinitiator ; acrylates ; epoxy ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Real time ultraviolet (RTUV) spectroscopy was used to study the photolysis kinetics of a radical-type morpholino initiator, during the polymerization of a multiacrylate monomer exposed to UV radiation in bulk, in solution, in a polyurethane-acrylate resin, and in a poly(methyl methacrylate) matrix. The photolysis rate constant k was determined from the exponential loss profile recorded; it was found to vary between 0.1 and 3s-1, depending on the light intensity and on the monomer concentration. The quenching of the photoinitiator excited states by the acrylate monomer was shown to be an important deactivation pathway which substantially reduces the rate of initiation. The observed influence of the film thickness and photoinitiator concentration on the k value were accounted for by the internal filter effect. Conversion versus time curves were recorded by real time infrared (RTIR) spectroscopy for the various systems examined, thus allowing a direct comparison of both the actual polymerization rate and the residual unsaturation content of the cured polymer. Various factors were shown to be responsible for the early stop of the polymerization, such as depletion of the photoinitiator, O2 inhibition, or vitrification of the polymer. The photoinitiated cationic ring-opening polymerization of a cycloaliphatic diepoxy monomer was also studied in real time by RTUV and RTIR spectroscopy. Despite a very fast photolysis of the triarylsulphonium initiator, the polymerization of the epoxy monomer developed less rapidly than for the acrylic monomer, with shorter kinetic chain lengths. A linear relationship was found to exist between the decay rate constant and the light intensity, for both the radical and the cationic photoinitiators, as expected for a direct photolysis process.
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    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 1077-1082 
    ISSN: 0887-624X
    Keywords: fluoroelastomers ; tetrafluoroethylene ; radiation ; terpolymerization ; kinetics ; mechanism ; properties ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Terpolymerization of tetrafluoroethylene (TFE) with propylene (P) and n-butyl vinyl ether (NBVE) induced by γ-rays at room temperature at dose rate 5 × 105 rad/h and P/NBVE molar ratio from 49/1 to 10/40 was carried out. An alternating copolymerization between TFE and two α-olefins was found to take place in this system, so that 50 mole % of TFE containing terpolymer is always formed at various monomer compositions. The terpolymer composition can be explained successfully by the treatment by a complex mechanism. The complex reactivity ratios of rI (TFE-complex) and rII (TFE-NBVE complex) were calculated to be 0.5 and 0.6, respectively, assuming a complex mechanism. The polymerization rate and molecular weight increase with NBVE concentration in the monomer mixture. Colorless transparent rubber-like polymers were obtained at each monomer composition. The glass transition temperature sharply decreases with NBVE concentration in the terpolymer but the thermal and chemical resistances of the terpolymer slightly decrease. Considering these results together with the mechanical properties it has been concluded that the 45/48/7 terpolymer of TFE/P/NBVE molar ratio is good as a practical elastomer useful at relatively low temperatures.
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    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 21-29 
    ISSN: 0887-624X
    Keywords: 4-methyl-2-oxetanone ; potassium cation-dibenzo-18-crown-6 counterion ; anionic polymerization ; kinetics ; 1H-NMR ; GPC ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization of 4-methyl-2-oxetanone (1) initiated with potassium acetate-dibenzo-18-crown-6 complex (2) in THF as solvent, was studied. Transfer reactions, leading to both crotonate anions and carboxylic acid formation, have been observed. Two kinetic effects of these reactions, hampering the living polymerization, have been established. The first results from reinitiation with the crotonate anions and thereby lowers the polymer molecular weight. The second is the decrease in the overall polymerization rate due to complexation of the growing carboxylate anions with carboxylic acid moieties. Kinetic scheme of polymerization involves propagation accompanied by transfer followed by slow reinitiation. This scheme, including complexation of the active species has been solved numerically. The apparent rate and equilibrium constants (kp, ktr, kri, and Kass and respectively) have been determined. Although these kinetic parameters depend strongly on the polymerization conditions, but the ratio of the rate constants kp : kt : kri is fairly constant and equal to 10-4 : 10-6 : 10-6, respectively (at 20°C). Conditions of the controlled anionic synthesis of the amorphous poly(4-methyl-2-oxetanone) with \documentclass{article}\pagestyle{empty}\begin{document}$\bar M_n$\end{document} as high as 1.7 × 104 and \documentclass{article}\pagestyle{empty}\begin{document}${{ \le \bar M_n } \mathord{\left/ {\vphantom {{ \le \bar M_n } {\bar M_n }}} \right. \kern-\nulldelimiterspace} {\bar M_n }} \le 1.20$\end{document} have also been elaborated.
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    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 2109-2120 
    ISSN: 0887-624X
    Keywords: epoxide ; reaction mechanism ; kinetics ; homopolymerization of epoxides ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of homopolymerization of the monofunctional epoxide N-methylglycidylaniline in the presence of a tertiary amine or an amino alcohol has been followed by reversed phase high performance liquid chromatography and size exclusion chromatography. The reaction products were identified by mass spectrometry using potassium ionization of desorbed species (K+IDS). 1,3-Di-N-methylanilino-2-propanol (P) was the main reaction product and low molecular weight oligomers with Mn 〉 600 were also formed. The molecular weight and fraction of oligomers decrease with increasing concentration of the initiator. The suggested complex reaction mechanism involves formation of four stable oligomeric series initiated by reaction of the epoxide with either an OH group of (a) the amino alcohol, (b) product P, (c) traces of water, or (d) the tertiary amine to form ionic species resulting in the ionic propagation. Regeneration of the initiator and formation of new initiating centers during the polymerization are the causes of low molecular weights of oligomers. © 1992 John Wiley & Sons, Inc.
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    Keywords: alginate ; polysaccharides ; kinetics ; oxidation ; permanganate ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics and mechanism of the [Alg.Mn VIO42-] intermediate complex formation during the oxidation of alginate polysaccharide at pHs ≥ 12 have been investigated spectrophotometrically. The reaction showed a first-order dependence in permanganate and a fractional order with respect to the alginate concentration (Alg). Kinetic and spectrophotometric evidence revealed the formation of manganate(VI) as transient species. The results obtained indicated the dependence of the rate of formation on the pH of the medium where the complex formation was base catalyzed. A mechanism consistent with the experimental results is discussed. © 1993 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 395-401 
    ISSN: 0887-624X
    Keywords: poly(di-t-Butyl fumarate) ; thermal decomposition ; kinetics ; autocatalysis ; solid-phase reaction mechanism ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Decomposition of t-butyl carboxylate (TBC) groups in a glassy poly(di-t-butyl fumarate) (PDTBF) at 140-170°C proceeds with a sharp acceleration caused by interchain interaction of TBC and carboxylic groups. According to selective dissolution data, at 70% degree of conversion the reaction system contains both unchanged PDTBF and a final product: poly(fumaric acid). For TBC groups decomposition in di-t-butyl fumarate (DTBF)-styrene copolymers above their Tg an apparent rate constant of autocatalysis increases with the increase of DTBF content in copolymer. Together with previously obtained x-ray data these results lead to conclusions about the topochemical character of the PDTBF decomposition. The mechanism suggested includes thermal decomposition of TBC groups (initiation), autocatalytic growth of spheric clusters up to a critical size (an appearance of primary germs of the new phase), and growth and branching of thread-like germs. A mathematical model based on these assumptions describes quantitatively the kinetic data. © 1993 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 831-839 
    ISSN: 0887-624X
    Keywords: Ziegler-Natta ; polymerization of ethylene ; high temperature ; kinetics ; vanadium ; oxidation state ; deactivation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetics of the polymerization of ethylene initiated by heterogeneous vanadium-based Ziegler-Natta catalysts (VCI3-1/3 AICI3) have been studied at high temperature (160°C, 5 bars) and compared with a titanium-based system. For the V catalyst, the dependence of the polymerization activity versus time, with the nature and the concentration of the associated aluminum alkyl, has been investigated. Kinetic results have also been correlated with the oxidation state of vanadium in the polymerization conditions. Despite the relatively high initial activity a low productivity is obtained; it can be attributed to a very fast deactivation of the active sites due to the reduction of vanadium III into vanadium II. The effect of the nature of the alkyl aluminum component of the catalytic system on the reduction process is shown. A kinetic model for the polymerization is proposed. © 1993 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 2205-2230 
    ISSN: 0887-624X
    Keywords: emulsion polymerization ; ethylene-vinyl acetate ; semi-batch emulsion ; copolymerization ; kinetics ; reactor design ; factorial experiments ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A good working knowledge of the mechanism and an appreciation of the effects the process variables have on the properties of interest are required for optimization and control of polymerization processes. Despite the importance of ethylene-vinyl acetate emulsion copolymers, limited kinetic information is available. Results from a series of factorial experiments are presented here which examine the emulsion polymerization of ethylene with vinyl acetate. Copolymers of up to 32 wt % ethylene have been produced at an ethylene pressure of 500 psig and a temperature of 20°C. The effects of the process variables on the rate of polymerization, copolymer composition, particle size and number, molecular weight averages, and gel content are discussed. The kinetic results obtained suggest process improvements for the production of homogeneous copolymer. Mechanistically, the locus of polymerization has been verified as the polymer particles and little water phase polymerization was observed. © 1993 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2165-2174 
    ISSN: 0887-624X
    Keywords: amic acid ; cyclic anhydride ; imidization ; kinetics ; model compounds ; polymer bound functional groups ; polymer-polymer reactions ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The validity of extrapolating the reactivity of low molar mass compounds in solution to the polymer-analogous chemistry between polymer-bound functionality is investigated for the reaction of primary amines with cyclic anhydrides in the moderately polar solvents, anisole and tetraethyleneglycol dimethylether. The kinetics of amic-acid formation and imidization of polymeric and small molecule mixtures measured by Fourier-Transform Infrared Spectroscopy at near-ambient and elevated temperatures are compared. A Significant decrease in both reaction rates is observed upon changing the primary amine from aliphatic to benzylic, benzylic to 1,2-diphenylethylamine, and 1,2-diphenylethylamine to polystyrene-bound 1,2-diphenylethylamine. Reasons for the influence of polymer-bound chemical functionality on the reaction rates for these amines are discussed. The imidization step is found to be rate limiting in the reaction of phthalic anhydride with benzylamine at the functional group concentrations reported (0.14M or less). © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2803-2812 
    ISSN: 0887-624X
    Keywords: 2-hydroxyethyl methacrylate ; kinetics ; redox initiation ; surfactants ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oxidation of ferrous orthophenanthroline (FeP) by peroxydiphosphate (PP) in aqueous medium at pH 1 was followed spectrophotometrically. Kinetic analysis has shown that oxidation occurs via the formation of an intermediate complex between FeP and PP. Equi-librium and rate constants were calculated. Influence of surfactants on the oxidation of FeP by PP was also Investigated. The equilibrium constant for complex formation was found to be higher in the presence of surfactants. The enhanced complex formation has been attributed to the ionic interactions between the charged surfactant and the ionic species in the reaction medium. Polymerization of HEMA initiated by the redox system,FeP/PP, was carried out in aqueous medium, under the conditions of excess reductant over oxidant and excess oxidant over reductant. The polymerization followed different mech-anisms under these conditions; with excess oxidant, the growing polymer radicals underwent oxidative termination, while with excess reductant, primary radical termination was pre-ferred. The effect of surfactants on the aqueous polymerization of HEMA using the redox system FeP/PP was also investigated. In addition to the decrease in rate, the polymerization followed a different mechanism in the presence of surfactants, the growing radicals ter-minated by mutual interaction. © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 515-520 
    ISSN: 0887-624X
    Keywords: pulsed laser polymerization ; kinetics ; solvent effects ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The homo- and copolymerizations of styrene (STY) and methylmethacrylate (MMA) have been studied in the presence of several levels of benzyl alcohol (BA). From pulsed laser polymerizations it has been found that the apparent propagation rate constant increased with increasing BA for all systems. In copolymerization it has been found that the reactivity ratios for STY decrease somewhat, but those for MMA change little with increasing BA. The tacticity of poly(MMA) formed in the presence of BA is affected, the amount of mm diads increasing with increasing BA. The results are interpreted as supporting the hypothesis that BA forms a strong complex with radical chain ends terminating in MMA and a weak complex with those terminating in STY. © 1997 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2177-2182 
    ISSN: 0887-624X
    Keywords: ring opening polymerization ; propylene oxide ; chitosan-supported rare earth complex ; kinetics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ring opening polymerization of propylene oxide in the presence of a new type of catalytic system composed of chitosan-supported rare earth complex, triisobutyl aluminium, and acetylacetone and its kinetics have been studied for the first time. It has been found that the characteristics of this catalytic system are of high catalytic activity, of higher stereoselectivity, and of a high molecular weight polymer of 2 × 106. Kinetic studies show that the polymerization rate is first order with respect to monomer concentration and catalyst concentration, respectively. The apparent activation energy of the polymerization reaction is 37.1 kJ/mol. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2177-2182, 1997
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 157-168 
    ISSN: 0887-624X
    Keywords: emulsion polymerization ; reaction calorimetry ; chain transfer agents ; kinetics ; radical desorption ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of chain transfer agents (CTA) on the emulsion copolymerization of styrene and butyl acrylate was studied in a bench scale 7 L reactor. On-line estimates of conversion were obtained through the joint use of calorimetric measurements and fast gravimetric data. Off-line measurements of partial conversions, molecular weight distribution (MWD), glass transition temperature (Tg), and particle diameter were also performed in order to investigate the effect of two mercaptans (tert-butanethiol and n-dodecanethiol) on both the kinetics of the polymerization process and the microstructure-dependent properties of the copolymer. The obtained experimental results were interpreted in terms of radical desorption and diffusive limitations of the CTA between the oil droplets and the particles. A model has been derived to compute the kinetic constants, the number of radicals per particle, and both the GPC/SEC diagrams and DSC thermograms related to MWD and Tg measurements, respectively. Several batch and semibatch examples are proposed to show that these important variables are satisfactorily fit by the model. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 157-168, 1998
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2653-2665 
    ISSN: 0887-624X
    Keywords: kinetics ; microwave cure ; thermal cure ; bisnadimide ; crosslinking ; mechanism ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetic studies of the crosslinking reaction of a nadic end-capped imide model compound, N,N′-(oxydi-3,4′-phenylene) bis(5-norbornene-2,3-dicarboximide), a bisnadimide, in thermal and microwave processes were investigated. The conversion of the endo isomer to exo isomer proceeds at a much lower temperature than the crosslinking reaction. The crosslinking reaction was monitored by the combined decrease in the infrared absorptions of the endo and exo isomers at 840 and 780 cm-1, respectively. The decrease in the concentration of starting materials follows first-order kinetics in the thermal and microwave processes. At the same temperatures (230 or 280°C), the crosslinking reaction proceeds at about 10 times faster in the microwave process than in the thermal process. Solid-state 13C-NMR showed no significant loss in C=C double bond resonance in the cured products by comparison with the starting material. This study provides direct evidence that the microwave process may be an efficient method to cure nadic end-capped polyimides. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2653-2665, 1998
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 665-673 
    ISSN: 0887-624X
    Keywords: epoxyacrylate ; diacrylates ; photopolymerization ; kinetics ; synergistic effect ; temperature effect ; heteroatom effect ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization kinetics of photocurable compositions based on an epoxyacrylate oligomer and three analogous diacrylate monomers were investigated. The effects of the oligomer-to-monomer ratio, curing conditions, and monomer structure were considered. The polymerization is characterized by a synergistic effect observed in a wide temperature range and occurring for the polymerization rate both in air and Ar and for final conversions in air. The final conversion in Ar is determined by viscosity of a formulation. The presence of a heteroatom (S or O) in the ester group of the reactive diluent is beneficial for the polymerization course, especially in air atmosphere. The best results were obtained for the sulfur-containing monomer. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 665-673, 1998
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  • 86
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    Biotechnology and Bioengineering 37 (1991), S. 967-972 
    ISSN: 0006-3592
    Keywords: papain ; organic solvent ; kinetics ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The effects of various concentrations of a water-miscible organic solvent [a 7:3 (v/v) mixture of N, N dimethylformamide and dimethylsulfoxide] on the kinetics of papain have been investigated. The parameters kcat and Km for the amidase and esterase activity of papain using N-α-benzoyl-DL-arginine-p-nitroanilide (BAPNA) and N-α-benzoyl-L-arginine ethyl ester (BAEE) as substrates were determined. For both types of activity, kcat initially increased (up to about 15% solvent), and then decreased with increasing concentrations of organic solvent. In contrast, Km increased sharply with the organic solvent concentration. Active site titration at 0 and 50% solvent indicated no change in the amount of active enzyme. Fluorometric measurements of the emission spectrum of papain did not indicate any major conformational changes with increasing concentrations of organic solvent.
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  • 87
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    Biotechnology and Bioengineering 40 (1992), S. 329-333 
    ISSN: 0006-3592
    Keywords: lipase ; supercritical carbon dioxide ; kinetics ; esterification ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Myristic acid esterification has been performed by an immobilized lipase from Mucor Miehei both in n-hexane and in supercritical carbon dioxide (SCCO2). The enzyme is stable in SCCO2 at 15 MPa and 323 K. The reaction rate is influenced by the concentration of water and by the reaction medium composition. A reaction mechanism is proposed, and kinetic parameters are determined at 12.5 MPa and 313 K. Maxium velocity appears 1.5-fold higher in SCCO2 than in n-hexane; however, as solubility of myristic acid is greater in n-hexane, it is not yet definitively clear that the supercritical medium is more favorable than the classical organic solvent for this type of enzyme reaction.
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  • 88
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    Biotechnology and Bioengineering 39 (1992), S. 629-634 
    ISSN: 0006-3592
    Keywords: biocatalyst ; cyanide degradation ; immobilized enzyme ; wastewaters ; kinetics ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: CYANIDASE@ is a new enzyme preparation capable of degrading cyanide in industrial wastewaters to ammonia and formate in an apparently one-step reaction, down to very low concentrations. This enzyme has both a high selectivity and affinity toward cyanide. A granular form of the biocatalyst was used in a recirculation fixed bed reactor in order to characterize the new biocatalyst with respect to pH, ionic strength, common ions normally present in wastewaters, mass transfer effects, and temperature. Long term stability was investigated. The kinetics of the enzymatic degradation of cyanide were studied in a batch reactor using the powdered immobilized enzyme preparation and modeled using a simple Michaelis-Menten equation.
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  • 89
    ISSN: 0006-3592
    Keywords: Modeling ; kinetics ; cyanobacteria ; photobioreactors ; Spirulina platensis ; mineral limitations ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A structured model for the culture of cyanobacteria in photobioreactors is developed on the basis of Schuster's approximations for radiative light transfer. This model is therefore limited to monodimensional geometries and kinetic aspects.Light-harvesting pigments play a crucial role in defining the profile of radiative transfer inside the culture medium and in controlling the metabolism, particularly the metabolic deviations induced by mineral limitations. Modeling therefore requires the biomass to be divided into several compartments, among which the light-harvesting compartment allows a working illuminated volume to be defined within the photobioreactor. This volume may change during batch cultures, largely decreasing as pigment concentration increases during growth but increasing as pigments are consumed during mineral limitation. This approach enables, in photobioreactors of simple parallelepipedic, geometries, kinetic parameters to be determined with high accuracy; this may then be extended to vessels of more complex geometries, such as cylindrical photobioreactors.The model is applied to controlled batch cultures of the cyanobacterium Spirulina platensis in parallelepipedic photobioreactors to assess its ability to predict the behavior of these microorganisms in conditions of light and mineral limitations. Results allowed the study of optimal operating condition for continuous cultures to be approached © 1992 John Wiley & Sons, Inc.
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  • 90
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    Biotechnology and Bioengineering 39 (1992), S. 790-793 
    ISSN: 0006-3592
    Keywords: biofilms ; kinetics ; steady state ; pseudoanalytical solution ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An extremely accurate pseudoanalytical solution for the flux of substrate into a steady-state biofilm is developed. The standard deviations between the substrate fluxes computed from the pseudoanalytical solution and the numerical solution were less than 2.6%. Additional advantages of the pseudoanalytical solution are that it has no inaccuracies around Smin* = 1 and it is composed of single continuous functions applicable to the whole Smin* region.
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  • 91
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    Biotechnology and Bioengineering 43 (1994), S. 267-274 
    ISSN: 0006-3592
    Keywords: microbial souring ; sulfate reduction ; porous media ; kinetics ; stoichiometry ; transport phenomena ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An anaerobic upflow porous media biofilm reactor was designed to study the kinetics and stoichiometry of hydrogen sulfide production by the sulfate-reducing bacterium (SRB) Desulfovibrio desulfuricans (ATCC 5575) as the first step for the modeling and control of formation souring (H2S) in oil field porous media. The reactor was a packed bed (50 × 5.5 cm) tubular reactor. Sea sand (140 to 375 μm) was used as the porous media. The initial indication of souring was the appearance of well-separated black spots (precipitates of iron sulfide) in the sand bed. The blackened zones expanded radially and upward through the column. New spots also appeared and expanded into the cone shapes. Lactate (substrate) was depleted and hydrogen sulfide appeared in the effluent.Analysis of the pseudo-steady state column shows that there were concentration gradients for lactate and hydrogen sulfide along the column. The results indicate that most of the lactate was consumed at the front part of the column. Measurements of SRB biomass on the solid phase (sand) and in the liquid phase indicate that the maximum concentration of SRB biomass resided at the front part of the column while the maximum in the liquid phase occurred further downstream. The stoichiometry regarding lactate consumption and hydrogen sulfide production observed in the porous media reactor was different from that in a chemostat. After analyzing the radial dispersion coefficient for the SRB in porous media and kinetics of microbial growth, it was deduced that transport phenomena dominate the souring process in our porous media reactor system. © 1994 John Wiley & Sons, Inc.
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  • 92
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    Biotechnology and Bioengineering 43 (1994), S. 865-873 
    ISSN: 0006-3592
    Keywords: Leuconostoc mesenteroides ; dextran ; kinetics ; bacterial profile modification ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Bacterial profile modification (BPM) is being developed as an oil recovery technique that uses bacteria to selectively plug oil depleted zones within a reservoir to divert displacing fluids (typically water) into oil-rich zones. Leuconostoc mesenteroides, which produces dextran when supplied with sucrose, is a bacterium that is technically feasible for use in profile modification. However, the technique requires controlled bacterial growth to produce selective plugging.A kinetic model for the production of cells and polysaccharides has been developed for L. mesenteroides bacteria. This model, based on data from batch growth experiments, predicts saccharide utilization, cell generation, and dextran production. The underlying mechanism is the extracellular breakdown of sucrose into glucose and fructose and the subsequent production of polysaccharide (dextran). The monosaccharides are then available for growth. Accompanying sucrose consumption is the utilization of yeast extract. The cell requires a complex media that is provided by yeast extract as a source of vitamins and amino acids. Varying the concentration ratio of yeast extract to sucrose in the growth media provides a means of controlling the amount of polymer produced per cell. Consequently, in situ bacteria growth can be controlled by the manipulation of nutrient media composition, thereby providing the ability to create an overall strategy for the use of L. mesenteroides bacteria for profile modification.
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  • 93
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    Biotechnology and Bioengineering 44 (1994), S. 194-204 
    ISSN: 0006-3592
    Keywords: biofilm ; biofilm reactors ; structure ; heterogeneity ; kinetics ; modeling ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A rotating annular reactor (Roto Torque) was used for qualitative and quantitative studied on biofilm heterogeneity. In contrast to the classic image of biofilms as smooth, homogeneous layers of biomass on a substratum, studies using various pure and mixed cultures consistently revealed more-dimensional structures that resembled dunes and ridges, among others. These heterogeneities were categorized and their underlying causes analyzed. Contrary to expectations, motility of the microorganisms not a decisive factor in determining biofilm homogeneity. Small Variations in substratum geometry homogeneity. Small variations in substratum geometry and flow patterns were clearly reflected in the biofilm pattern. Nonhomogeneous flow and shear patterns in the reactor, together with inadequate mixing resulted in significant, position-dependent differences in surface growth. It was therefore not possible to take representative samples of the attached biomass. Like many other types of reactors, the Roto Torque reactor is valuable for qualitative and morphological biofilm experiments but less suitable for quantitative physiological and kinetics studies using attached microorganisms. © 1994 John Wiley & Sons, Inc.
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  • 94
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    Biotechnology and Bioengineering 47 (1995), S. 277-287 
    ISSN: 0006-3592
    Keywords: phosphorus removal ; biological ; kinetics ; metabolic model ; polyphosphate ; PHB ; glycogen ; batch reactor, sequenced ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A structured metabolic model is developed that describes the stoichiometry and kinetics of the biological P removal process. In this approach all relevant metabolic reactions underlying the metabolism, considering also components like adenosine triphosphate (ATP) and nic-otinamide-adenine dinucleotide (NADH2) are describedbased on biochemical pathways. As a consequence of the relations between the stoichiometry of the metabolic reactions and the reaction rates of components, the required number of kinetic relations to describe the process is reduced. The model describes the dynamics of the storage compounds which are considered separately from the active biomass. The model was validated in experiments at a constant sludge retention time of 8 days, over the anaerobic and aerobic phases in which the external oncentrations as well as the internal fractions of the relevant components involved in the P-removal process were monitored. These measurements include dissolved acetate, phosphate, and ammonium; oxygen consumption; poly-β-hydroxybutyrate (PHB); glycogen; and active biomass. The model satisfactorily describes the dynamic behavior of all components during the anaerobicand aerobic phases.© 1995 John Wiley & Sons, Inc
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  • 95
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    Biotechnology and Bioengineering 48 (1995), S. 246-256 
    ISSN: 0006-3592
    Keywords: polyethylene glycol ; phosphate ; phase separation ; kinetics ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Phase separation times for polyethylene glycol (PEG)-4000-phosphate aqueous two-phase systems were studied, for small scale (5-g) and large scale (1300-g) systems, as a -function of the stability ratio. Profiles of dispersion height for both large and small scale systems were represented as a fraction of the initial height and were found to be independent of the geometrical dimensions of the separator. Furthermore, by plotting time as a fraction of the initial height the total time of separation can be calculated for a given height of system at a particular stability ratio. This generalization is important for the design of large scale aqueous two-phase separators. Phase separation times were also found to be dependent on which of the phases is continuous. A characteristic change in phase separation time was also observed at the phase inversion point (i.e., where the dispersed phase changes to a continuous phase and vice versa) and this point tends toward higher volume ratios as the tie-line length (TLL) is increased. Furthermore, the phase inversion point at each TLL corresponds to a fixed phosphate concentration. © 1995 John Wiley & Sons, Inc.
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  • 96
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    Biotechnology and Bioengineering 38 (1991), S. 1020-1028 
    ISSN: 0006-3592
    Keywords: hybridoma ; cell culture ; continuous culture ; kinetics ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A hybridoma cell line, AFP-27-P, was cultivated in continuous culture under glucose-limited conditions. The viable cell concentration, dead-cell concentration, and cell volume all varied with the dilution rate. A model previously developed for a nonproducing clone of the same cell line, AFP-27-NP, was extended to describe the behavior of the cells. The relationship between the specific growth rate and glucose concentration is described by a function similar to the Monod model. A threshold glucose concentration and a minimum specific growth rate are incorporated; the model is meaningful only at glucose concentration and a minimum specific growth rate are incorporated; the model is meaningful only at glucose concentrations and specific growth rates above these levels. The relationship between the death rate and the glucose concentration is described by an inverted Monod-type function. Furthermore, the yield coefficient based on glucose is constant in the lower range of specific growth rates and changes to a new constant value in the upper range of specific growth rates. No maintenance term for glucose consumption is used; in the plot of specific glucose consumption rate vs. specific growth rate, the line intercepts the specific growth rate at a value close to the minimum growth rate. The productivity of antibody as a function of the specific growth rate is described by a mixed type model with a noon-growth-associated term and a negative-growth-associated term. The values for the model parameters were determined from regression analysis of the steady state data.
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  • 97
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    Biotechnology and Bioengineering 40 (1992), S. 1328-1336 
    ISSN: 0006-3592
    Keywords: immobilization ; papain ; alumina ; kinetics ; fluorescence ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Particulate aluminum oxides (alumina) were examined as supports for the immobilization of the proteolytic enzyme papain. Two alumina supports termed C1 and CPC were derivatized using organic phosphate linkers to create free carboxyl groups using a two-step process. Papain binding to these derivatized aluminas was performed using the water soluble carbodiimide 1-ethyl-3-(dimethylaminopropyl) carbodiimide. Reactions were optimal at 10 mM carbodiimide. The immobilized protein showed similar kinetic constants when compared to the solution protein. The pH dependence and thermal stability were essentially identical. The immobilized papain showed a blue shift in the intrinsic fluorescence emission maxima. Papain modified with the active site-specific fluorescent probe acrylodan showed overlapping emission maxima. These results are interpreted as retention of the hydrophobic environment of the active site with a perturbation in the structure of the rest of the protein caused by its association with the negatively charged surface. © 1992 John Wiley & Sons, Inc.
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  • 98
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    Biotechnology and Bioengineering 41 (1993), S. 370-379 
    ISSN: 0006-3592
    Keywords: immobilized cell ; kinetics ; Monod growth Kinetics ; substrate utilization kinetics ; physicochemical effects in immobilized cell culture ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A methodology is described for measurement if immobilized and suspended cell growth and substrate utilization kinetics parameters. Substrate utilization and growth kinetics were compared between immobilized and suspended cells for toluene degrading Pseudomonas strains K3-2 and 2,4-dichlorophenoxyacetic acid (2,4-D) degrading strain DBO131(pR0101), respectively. Kinetic parameters were estimated using nonlinear parameter estimation methods and compared between the immobilized and suspended Pseudomonas cells to determine the effect of immobilization on cellular growth and substrate utilization. Factors influencing the experimental design included calculated oxygen flux rates, primary carbon substrate flux rates, and shear stresses on the immobilize cell. Statistical interpretation of the cellular reaction rate parameters indicates that only the growth kinetics of the toluene system were significantly altered upon immobilization. Substrate utilization kinetics remained unchanged upon immobilization. The substrate growth associated half-saturation constant (Kg) for the toluene system increased by 30-fold and the maximum specific growth rate (μmax) decreased by 2-fold upon immobilization. Implication of these results for experimental determination of cellular kinetic parameters and for immobilization cell bioreactors design are discussed. © 1993 John Wiley & Sons, Inc.
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  • 99
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    Biotechnology and Bioengineering 42 (1993), S. 247-250 
    ISSN: 0006-3592
    Keywords: hybridoma ; antibody productivity ; kinetics ; instability ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An immunoglobulin G (IgG2b) producing hybridoma cell line (S3H5/γ2bA2) was cloned and subcloned. Twenty subclones were grown in parallel while being adapted in a stepwise fashion to serum-free medium. Following adaptation to serum-free medium, it was found that 16 of the 20 subclones remained at a relatively constant proportion of nonproducing cells. Three of the remaining subclones transiently deviated from this balance but eventually returned toward this population composition. One subclone continued to lose productivity. A population balance was reached at approximately 8% of the population being nonproducers. The loss of antibody productivity was thus highly reproducible. © 1993 John Wiley & Sons, Inc.
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  • 100
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    Biotechnology and Bioengineering 43 (1994), S. 1081-1086 
    ISSN: 0006-3592
    Keywords: solvation ; organic media ; kinetics ; subtilisin ; thermodynamics ; solubility ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Subtilisin Carlsberg adsorbed on silica particles has been used to catalyze the transesterification of CBZ-Ala-ONp and CBZ-Leu-ONp with 1-butanol in organic systems preequilibrated to water activity of 0.93. Initial reaction rates are conveniently followed by extraction of the released nitrophenol into an alkaline aqueous phase. Kinetic parameters were determined for varied ester concentrations in toluene, isopropyl ether, and hexane. The effect of solvent on substrate solvation was determined by solubility measurements. Much of the observed effect of solvent on Vm/Km may be accounted for by solvation differences. The residual effect of solvent on Km, after discounting solvation differences, is completely opposite to the apparent trend. © 1994 John Wiley & Sons, Inc.
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