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  • 1
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 26 (1988), S. 1937-1959 
    ISSN: 0887-624X
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Batch emulsifier-free copolymerizations of styrene (S) and butyl acrylate (BuA) have been performed for a S/BuA weight ratio = 50/50 in the presence of two types of functional comonomers [methacrylic acid (MAA) at different pHs] or potassium sulfopropylmethacrylate (SPM) and two initiators [potassium persulfate or 4-4′azobiscyanopentanoic acid (AZO)]. The use of AZO/MAA system results in the formation of polymer particles with only surface carboxylic end groups. The particle size of the final latexes can be adjusted with the MAA concentration, provided the polymerization is carried out at pH 〉 6.5. However, the higher the MAA concentration, the sooner the polymerization levels off in conversion. With the K2S2O8/SPM system, particles bearing only sulfate and sulfonate groups are produced and the polymerization is complete. In that case, the particle size of the final latexes is smaller than with the previous system and 30% of the SPM is fixed on the particle surface, instead of 10% with MAA. Using SPM, a too high functional monomer concentration results in the latex destabilization caused by the formation of a large amount of polyelectrolytes. Kinetic studies indicate that most of the functional monomer is incorporated onto the particle surface during the last 30% conversion of the polymerization. A tentative explanation of such a behavior is discussed, based on the existence of two polymerization loci in the latex system.
    Zusätzliches Material: 12 Ill.
    Materialart: Digitale Medien
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  • 2
    ISSN: 0887-624X
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Soapless emulsion copolymerization of styrene (S) and n-butyl acrylate (BuA) has been investigated using two types of initiator and different comonomer feed mixtures. When using K2S2O8 as initiator, the particle size and size distribution of the final latexes (500 nm and 1.003, respectively) is not significantly affected by the comonomer feed composition, whereas the molecular weight and surface characteristics were found to sharply change at high butyl acrylate content. Based on the most probable particle nucleation mechanism and type of chain termination in the monomer swollen particles, a tentative explanation of these results has been proposed. Replacing persulfate by a carboxylic initiator (4-4′-azobiscyanopentanoic acid) results in the formation of stable particles as α observed with the persulfate, provided the aqueous phase pH is fixed in between 6 and 7. Results on the initiator residue location as a function of the conversion point out that the particle flocculation mechanism is strongly significant in the preparation of such latexes.
    Zusätzliches Material: 13 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1271-1281 
    ISSN: 0887-624X
    Schlagwort(e): potassium persulfate ; decomposition ; soap-emulsified systems ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Two methods of analysis, potentiometry and capillary electrophoresis, were used to study the decomposition of potassium persulfate (KPS) in aqueous solutions. The experiments were carried out in a glass reactor equipped with continuous control of temperature and pH during the reaction. The effect of the pH on the decomposition of KPS was investigated. The rate of KPS decomposition in the presence of a variety of additives (surfactants, inhibitor, monomer-like molecules, and monomers), which are used in emulsion polymerization recipes, was also studied over the temperature range of interest. The rate of disappearance of the persulfate ion was greatly increased in the presence of hydroquinone, but changed very little in the presence of surfactants. © 1996 John Wiley & Sons, Inc.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 4
    ISSN: 0887-6258
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 5
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 28 (1990), S. 137-152 
    ISSN: 0887-624X
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Emulsion terpolymerization of styrene (S), butylacrylate (BuA) and sodium acrylamido undecanoate (AUNa), a surface active functional monomer have been carried out using a batch process in the presence of sodium 4-4′-azobiscyanopentanoate as initiator. Varying the AUNa concentration, stable particles bearing only carboxylic charges have been produced with diameters ranging from 200 to 500 nm at solids content as high as 40%. However a low AUNa yield at the particle surface has been found (30-35%), which could be explained by very unfavorable reactivity ratios of AUNa with S and BuA. Most of the AUNa seems to be wasted in the water phase (unpolymerized and forming hydrosoluble chains). Furthermore, a concentration of AUNa higher than 10-2 mol L-1 results in the latex destabilization, presumably caused by the formation of a large amount of polyelectrolytes. Kinetic studies of the AUNa consumption show that the AUNa is mainly fixed at the particle surface between 90 and 100% conversion, which indicates that the AUNa is mainly polymerized in the water phase and not at the particle surface. An attempt has been made to increase the surface charge density by polymerizing a shell of AUNa/S/BuA on a seed latex. It turned out to be unsuccessful (low surface yield, formation of new particles).
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 6
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 157-168 
    ISSN: 0887-624X
    Schlagwort(e): emulsion polymerization ; reaction calorimetry ; chain transfer agents ; kinetics ; radical desorption ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 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
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 7
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Polymers for Advanced Technologies 6 (1995), S. 465-472 
    ISSN: 1042-7147
    Schlagwort(e): polystyrene, emulsion polymerization ; styrenic nonionic surfactant ; latex stability ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Among the variety of possible structures for polymerizable surfactants, it seems clear that the most interesting should be those with the reactive group located in the hydrophobic part of the molecule. We report here a study based on such a surfactant. Its general formula is \documentclass{article}\pagestyle{empty}\begin{document}$$ CH_2d\hbox{---}CH\hbox{---}C_6 H_4\hbox{---}CH_2\hbox{---}O(CH_2)_n\hbox{---}O(CH_2CH_2\hbox{---}O)_m\hbox{---}H $$\end{document}A set of surfactants has been produced with m varying from 23 to 48 and n = 6 or 12. The compounds have been characterised by 1H-NMR (nuclear magnetic resonance), size exclusion chromatography, surface tension measurements and turbidimetry.These surfactants have been copolymerized with styrene in emulsion polymerization. The coagulum is rather important, except if m is large enough. Although the incorporation of the surfactant in the latex is rather high. Most of the anchored surfactant remains at the surface and is not too buried inside. The particle size decreases with both the amount of surfactant and the length of its hydrophilic part. The use of these polymerizable surfactants leads to an excellent stability of the latex against the addition of electrolytes, and also against freeze-thawing constraints.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 8
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Polymers for Advanced Technologies 6 (1995), S. 473-479 
    ISSN: 1042-7147
    Schlagwort(e): emulsion polymerization ; steric stabilization ; polymeric transfer agent ; redox system ; polystyrene colloids ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Thiol-ended polyethylene oxide (I) has been prepared from the esterification of thioglycolic acid with monomethylether of polyoxyethylene glycol. Emulsion polymerization of styrene (and, in a few cases, methylmethacrylate as comonomer) was carried out in the presence of I using either water-soluble azo initiator or t-butylhydroperoxide. In the former case, bimodal particle size distribution was obtained while monodisperse latexes could be prepared in the latter case. Then a redox system was formed from I and t-BuOOH so that I was both an initiator and a transfer agent. Good steric stabilization of the latexes was observed. The polyethylene oxide sequence of I was partly incorporated at the surface of the latex particles, but the incorporation yield remained limited (between 7 and 18%). Most of the resdue of I remained in the serum.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 9
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 52 (1994), S. 1823-1832 
    ISSN: 0021-8995
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Physik
    Notizen: To measure the polymer/monomer interaction parameter as a function of composition, a set of partially cross-linked synthetic latices has been produced by batch and semicontinuous emulsion polymerization. The degrees of cross-linking have been measured by DMA and also predicted by computer simulation based on kinetic data. With equilibrium monomer swelling experiments achieved on films made from these polymers, two curves of the interaction parameter vs. the polymer fraction have been computed. These curves compare favorably with a theoretical model based on a Unifac procedure for the estimation of monomer activity. Two different data bases, liquid-liquid and liquid-vapor equilibria, have been used in the Unifac model. For the polystyrene/n-butyl methacrylate system, a linear relationship found between the interaction parameter and composition is both predicted and measured experimentally. In all cases, this interaction parameter is found to increase with polymer concentration. © 1994 John Wiley & Sons, Inc.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 10
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 53 (1994), S. 1469-1476 
    ISSN: 0021-8995
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Physik
    Notizen: The possibility of measuring in situ the interfacial tension at the monomer-swollen polymer-water interface of synthetic latices is considered in detail. Experimental measurements of certain liquid or vapor phase properties of the latex can, in principle, yield values of the desired interfacial tension. This technique requires the evaluation and comparison of the Flory-Huggins term and the Morton term of the thermodynamic expression for the chemical potential of the monomer in the latex particle. While each term can be evaluated, it turns out that the relative magnitudes of the two terms are such that unrealistically high precision is required in the experimental measurements for this technique to be useful for obtaining reasonably accurate interfacial tensions. At saturated swelling conditions with highly surface-active emulsifiers (e.g., sodium dodecyl sulfate), the interfacial tension values obtained have a precision of only about ±50%. The reliability of these approximate values degrades rapidly as one moves away from saturation conditions, so as to render in situ experimental techniques inappropriate for gaining accurate knowledge about the surface energy at the latex particle-water interface at any monomer-polymer ratio. © 1994 John Wiley & Sons, Inc.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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