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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 191 (1990), S. 1565-1573 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A kinetic model of the homogeneous anionic polymerization of 1,4-divinylbenzene (1,4-DVB) in dilute solutions with instantaneous initiation and without cyclization and termination reactions is proposed. The monomer and pendant vinyl group conversions, degrees of polymerization of the primary chains and the crosslinking densities were predicted as a function of the reaction time as well as 1,4-DVB and initiator (butyllithium) concentrations. The previous experimental data concerning the formation of the microgels can be explained using the kinetic mechanism of the polymerization reaction and neglecting cyclization. Calculations indicate that reactive 1,4-DVB microgels can be synthesized in the whole concentration range of the initiator.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 189 (1988), S. 2201-2217 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The free-radical copolymerization of styrene with small quantities of a commercial DVB (conc.: 0,35 to 0,53 mol-% DVB) was carried out at 70°C in bulk or in concentrated toluene solution. The extent of the crosslinking reactions beyond the gel point and the structural characteristics of the resulting networks were examined using equilibrium swelling in toluene and gel fraction measurements. The copolymerization reactions yield loosely crosslinked networks together with varying amounts of soluble polymer. The experimental results concerning the formation of the networks and their properties can be explained using the kinetic mechanism of the copolymerization reaction and neglecting cyclization. At a low degree of initial dilution, two opposing effects of the diluent, namely dilution and plasticizing effects, were found to determine the properties of the networks. Calculations using the theory of rubber elasticity indicate that considerable amounts of free chain ends are present in the networks. The crosslinking efficiency was found to decrease, but the size of the primary chains and that of the network chains increase with increasing degree of initial dilution.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 157 (1988), S. 1-13 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Porositätsbildung bei der Suspensionscopolymerisation von Styrol/Divinylbenzol (S-DVB) in Toluol-Cyclohexanol-Mischungen Wurde untersucht. Die Porosität der Copolymeren wächst, und ihr Quellverhalten nimmt ab, wenn der DVB-Gehalt in der Ausgangsmischung ansteigt und die Lösefähigkeit des Mediums abnimmt. Es wurde gefunden, daß der Volumenruch des aus dem Netzwerk ausgeschiedenen Lösemittel vD, konstant wird, wenn eine kritische Menge an DVB und Lösemittel überschritten ist. Dieser Grenzwert für vD ist nur vom Lösungsparameterunterschied zwischen Lösemittel und Polymerem, abhängig. So kann, wenn genügende Mengen an DVB und Lösemittel zugegen sind, die maximale Porosität der S-DVB-Copolymeren aus den Lösungsparametern der Komponenten vorausgesagt werden.
    Notes: Porosity formation by suspension copolymerization of styrene-divinylbenzene (S-DVB) in toluene-cyclohexanol mixtures was investigated. The total porosity of the copolymers increases and their volume swelling ratio in toluene decreases as the DVB concentration in the starting monomer mixture increases and the solvating power of the polymerization medium decreases. The volume fraction of the diluent separated out of the network phase, vD, was found to be constant after passing a critical amount of DVB and the diluent. The limiting value of vD is only dependent on the solubility parameter difference of the polymer and the diluent. Thus, if sufficient amounts of DVB and diluent are present during the network formation, the maximum porosity of S-DVB copolymers can be predicted from the solubility parameters of the components.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 157 (1988), S. 15-21 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Porenstabilität von Styrol-Divinylbenzol-Copolymeren (S-DVD), hergestellt in Toluol-Cyclohexanol-Mischungen, wurde in Abhängigkeit von der DVB-Konzentration, der Lösemittlezusammensetzung und der Verdünnung untersucht. Die Stabilität der Porenstrukturen nimmt mit steigender DVB-Konzentration zu und - in gewissem Ausmaß - auch mit steigender Verdünnung. Bei einem festgelegten Grad der Gleichgewichtsquellung in Toluol nimmt die Porenstabilität auch mit steigender Lösefähigkeit des Verdünnungsmittels zu. Die Dichte der S-DVB-Copolmeren steigt während der Sulfonierung mit Chlorsulfonsäure an, aber die Stabilität der Poren bleibt unverändert.
    Notes: The pore stability of styrene-divinylbenzene (S-DVB) copolymers prepared in toluene-cyclohexanol mixtures as inert diluents was investigated as a function of the DVB concentration, diluent composition, and dilution. The stability of the porous structures increases with increasing DVB concentration and, to some extent, with increasing dilution. At a fixed degree of equilibrium volume swelling in toluene, the pore stability also increases with increasing with increasing solvating power of the diluent. The density of S-DVB copolymers increases during the sulfonation reaction with chlorosulfonic acid, but the stability of porosity remains unchanged.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 153 (1987), S. 125-134 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Inhomogenität in der Zusammensetzung und der mittlere Quellungsgrad von heterogenen Styrol-Divinylbenzol-Copolymeren (S-DVB) wurden mit Hilfe von zwei morphologischen Eigenschaften der porösen Copolymeren untersucht. Für einen bestimmten Volumenbruch eines nicht-solvatisierenden Verdünnungsmittels steigt die Inhomogenität mit zunehmender DVB-Konzentration an. Außerdem nimmt die Vernetzungsdichte der schwach vernetzten Bereiche des Netzwerkes mit zunehmender DVB-Konzentration ab. Die experimentellen Ergebnisse werden durch das Mikrogel-Modell für die Netzwerk-Bildung erklärt. Der mittlere Volumenquellungsgrad kann aus der Zusammensetzung des anfänglichen Monomerengemisches und aus der Porosität des getrockneten Copolymeren vorhergesagt werden. Die änderungen in v2, dem Volumenbruch des Polymeren im gequollenen Gel, und die Bedingungen für die Poren-Stabilität werden in Abhängigkeit von diesen Parametern diskutiert.
    Notes: The compositional inhomogeneity and the average degree of swelling of heterogeneous styrene-divinylbenzene (S-DVB) copolymers were investigated using two morphological features of porous copolymers. At a fixed volume fraction of a nonsolvating diluent, the extent of inhomogeneous crosslinking increases with increasing DVB concentration. In addition, the crosslinking density of less crosslinked regions of the network decreases as the DVB concentration increases. The experimental results can be explained by the microgel-model of the network formation. The average degree of volume swelling can be predicted from the composition of the starting monomer mixture and from the porosity of the final copolymer dried from water. Depending on these parameters, the changes in the value of v2, the volume fraction of copolymer in the swollen gel, and the conditions for the pore stability are discussed.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Theory and Simulations 3 (1994), S. 417-426 
    ISSN: 1022-1344
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A kinetic model is presented for prediction of the gel properties in free-radical monovinyldivinyl monomer copolymerization. It is an extension of the kinetic model proposed recently for the sol species. The model involves the moment equations of the primary chains in the gel, and predicts the gel growth and structure as a function of the reaction time. Formulae for the chain length averages of the primary chains in the sol and in the gel were derived. The equations for calculating the number- and weight-average primary chain lengths are identical to the equations derived by statistical methods.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Theory and Simulations 4 (1995), S. 967-981 
    ISSN: 1022-1344
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A kinetic model was used to predict the molecular weight developments and the critical properties in free-radical crosslinking copolymerization. The predictions of the model were compared to the experimental data reported previously. Agreement of the kinetic model with experiments is satisfactory for both low and high crosslinker contents. The model parameters indicate increasing extent of shielding of pendant vinyl groups as the reaction proceeds due to the increasing number of multiple crosslinkages. The calculation results indicate that the real critical exponents can only be observed in the region ε 〈 10-2-10-3 where experimental studies are very difficult. Outside of this region, the apparent critical exponent γ describing the divergence of the weight-average molecular weight was found to deviate from the classical value due to the conversion dependent kinetics of free-radical crosslinking copolymerization.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 61 (1996), S. 485-493 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The influences of polymerization temperature, initiator and monomer concentrations, ionic strength of the aqueous phase, as well as ethylene glycol dimethacrylate (EGDM) co-monomer, on the kinetics of the emulsifier-free emulsion polymerization of methyl methacrylate (MMA) and on the properties of the resulting poly(methyl methacrylate) (PMMA) lattices were studied. The polymerizations were carried out using potassium persulfate (KPS) as the initiator. Monodisperse PMMA lattices with particle diameters varying between 0.14-0.37 μm and polymer molecular weights of the order 0.4 × 106 to 1.2 × 106 g/mol were prepared. The initial rate of polymerization increases with increasing temperature, KPS-MMA mole ratio, EGDM content, or with decreasing ionic strength of the aqueous phase. It was shown that the bead size can be limited by reducing the monomer concentration or by using the cross-linking agent EGDM. The ionic strength of the aqueous phase has a dominant effect on final particle diameter and polymer molecular weight. The uniformity of the latex particles increases as the temperature increases or as the initiator concentration decreases. The experimental results can be reasonably interpreted by the homogeneous nucleation mechanism of the emulsifier-free emulsion polymerization of MMA. © 1996 John Wiley & Sons, Inc.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 46 (1992), S. 401-410 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Porous poly(2-hydroxyethyl methacrylate) (PHEMA) beads cross-linked with ethylene glycol dimethacrylate (EGDM) were prepared by the suspension polymerization of the monomers in the presence of cyclohexanol or toluene as the diluents. A 20% aqueous NaCl solution containing MgCl2 · 6H2O, bentonite, and gelatine was used as the water phase. In this way, spherical, highly swellable, and/or porous copolymer beads of sizes 0.1-1.0 mm could be synthesized at EGDM contents higher than 20 mol %. The copolymers formed in cyclohexanol, compared to those prepared in the absence of a diluent, exhibit a larger degree of volume swelling in water, indicating that most of the diluent remains in the gel phase throughout the copolymerization. Contrarily, toluene induces porous structures even at a very low degree of cross-linking (41% porosity at 2 mol % EGDM). An interesting feature of HEMA-EGDM copolymerization in toluene is that the pore volume of the networks increases with increasing EGDM concentration up to 20 mol %, but it decreases again as the EGDM concentration further increases. The results can be explained with the differences in the solvating conditions of the copolymers depending on their EGDM contents.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 46 (1992), S. 421-434 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The relationships between the synthesis conditions and the morphology of ethylene glycol dimethacrylate (EGDM) networks were investigated. EGDM networks were prepared by free-radical polymerization in toluene as a diluent. The networks were characterized by swelling, porosity, and pendant vinyl group content measurements. The accessibility of pendant vinyls to low molecular weight compounds was tested using pyrrolidine as a model reactant. The results show that the polymerization of EGDM in toluene is accompanied by a phase separation in the system. The networks thus obtained are heterogeneous and exhibit an inhomogeneity in the porosity and swelling distributions. Both the weight swelling ratio and the pore volume of the networks increase with increasing monomer dilution. It was also found that the accessibility of pendant vinyls increases as the cross-linking density of the network decreases or as its porosity increases. The results can be explained with the formation of highly cross-linked microgels as the intermediates in the network formation processes. Two equations were derived to predict the equilibrium weight swelling ratio and the pore volume of heterogeneous networks. Satisfactory agreement of the results of measurements with the predictions of the equations was observed.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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