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  • 1
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 24 (1986), S. 133-145 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ortho-vinylbenzaldehyde has been prepared in a three-step synthesis. Vacuum-degassed monomer was polymerized with azodiisobutyronitrile initiator in bulk and in solution in 2-butanone. The kp/kt1/2 value at 60°C is 4.7 × 10-2 L1/2 mol-1/2s-1/2. This is about twice the ratio for styrene. Chain transfer to monomer appears to be significant. Insoluble, crosslinked products were produced at high conversions, because of chain transfer to polymer. Tg of poly(ortho-vinylbenzaldehyde) was found to be 142°C.Polymers made under N2 atmosphere often contained acetal groups. These can be produced by acid catalysis in the presence of small concentrations of ortho-vinylbenzyl alcohol. A laddertype structure is produced.The monomer is capable of photoinitiation. Insoluble gels were produced in bulk monomer at all conversions. The initiation rate was very high and crosslinking resulted from combination of radicals produced from photolysis of the pendant 0-benzaldehyde groups in the macromolecules.
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 437-441 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 1409-1417 
    ISSN: 0887-624X
    Keywords: emulsion polymerization ; oligomers ; polystyrene ; hydrotalcite ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dominant species in the early stages of an emulsifier-free emulsion polymerization of styrene has been found to be an oligomer of two to three monomer units using a novel trapping technique. This involved the intercalation of charged primary oligomers between the layers of a hydrotalcite, [Mg4Al2(OH)12]2+[A]2- (where A = dianion). Hydrotalcites are an important class of lamellar, inorganic compounds whose interlayer spacing can be mod-ified by anion exchange. Our approach first involved preparing a hydrotalcite precursor in which the layers were propped apart by an organic dianion (terephthalate = TA). This material was then used to capture the negatively charged polystyrene oligomers from the emulsion polymerization reaction mixture. We found that TA was rapidly ion-exchanged for the charged oligomers.The resulting pillared hydrotalcite material was characterized using XRD and SEC. We found that the interlayer spacing between the hydroxide layers increased to 23.2 Å on exposure to the emulsion reaction mixture. This represents an interlayer expansion of 18.3 Å (after subtraction of the hydroxide layer contribution), which is cnsistent with intercalation of oligomers with two to three monomer units arranged in a bilayer. This size estimate was confirmed by the results of size exclusion chromatography. © 1995 John Wiley & Sons, Inc.
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  • 4
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 1849-1857 
    ISSN: 0887-624X
    Keywords: emulsion polymerization ; acrylic polymers ; core shell ; supermicron ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The emulsion polymerization of large MMA/BA copolymer particles with narrow particle size distributions and core-shell structure is described. A series of sequential seeded growth emulsion polymerizations were used to obtain monodisperse particles with diameters of at least 3 μm, at 30% solids contents. Because the core and shell polymers used here were chemically similar, core-shell structures could not be verified by differential staining tech-niques. Core-shell structure was demonstrated by minimum film-forming temperature studies and by scanning electron microscopy in conjunction with energy dispersive x-ray analysis, using chlorine-labeled core polymers. © 1995 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 34 (1996), S. 3061-3069 
    ISSN: 0887-624X
    Keywords: aggregation ; emulusion polymerization ; flocculation ; latex ; particles ; polymer ; size distribution ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The basic features of a three-step experimental process to produce supermicron polymer particles are described. First, a submicron emulsifier-free latex is prepared by a well-known technique. Second, the latex is aggregated by destabilizing with cetyl pyridinium chloride under constant stirring conditions, to yield roughly spherical clusters of 6-12 μ diameter. Third, the aggregates are stabilized with poly(vinyl alcohol) and internally coalesced by heating at or above the glass transition temperature. The final product particles have relatively smooth surfaces. Results are qualitatively interpreted in terms of a dynamic equilibrium where the aggregate size is determined by a balance between attractive interparticle potentials and stirring shear forces. Bimodal aggregate size distributions suggest the aggregate break-up mechanism may involve the erosion of individual latex particles and small fragments from the surface of aggregates. © 1996 John Wiley & Sons, Inc.
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  • 6
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 1597-1606 
    ISSN: 0887-624X
    Keywords: emulsion polymerization ; surfactants ; oligomers ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is well known that the amount of surfactant must be carefully controlled during starve-fed emulsion polymerization processes. Too little surfactant leads to emulsion instability and coagulation, while too much surfactant leads to secondary particle formation. Although these relationships are qualitatively understood in the art, there is little quantitative basis to guide the synthetic chemist, especially in multistep starve-fed emulsion polymerization processes to make larger supermicron particles. We have developed a method, which will be described in a companion article, to control the surfactant level by monitoring the surface tension during polymerization. In order to quantitatively predict how much surfactant to add at any given time, one needs to know in advance the adsorption characteristics of the soap. Further complicating the matter is the formation of “in situ” or oligomeric surfactant during polymerization with aqueous initiators such as ammonium persulfate.This work demonstrates how to prepare surface-active oligomers and how to make latex particles using them as surfactant. First, we established the mass balance for the initiator-derived sulfate groups in seed latexes by conductometric, potentiometric, and iodometric titrations. Based on the characterization of seed latexes, a method for determining the effective sulfate concentration has been developed. When surface-active oligomers were used as the only surfactant, we obtained a series of monodisperse, supermicron copolymer latex particles with diameters up to 3.22 μm. This is a similar result to that obtained with a commercially made anionic surfactant. © 1995 John Wiley & Sons, Inc.
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  • 7
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2297-2304 
    ISSN: 0887-624X
    Keywords: methyl methacrylate ; emulsion polymerization ; in situ surfactant ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A “surfactant-free” emulsion polymerization of methyl methacrylate was conducted at 80°C with ammonium persulfate initiator. The water-soluble MMA-based oligomers re-maining were isolated and analyzed both as-produced and after hydrolysis. NMR analysis revealed that the mole ratio of MMA repeat units to sulfate end groups in the former is 6.5. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and gel permeation chromatography both showed that the mean number of MMA repeat units comprising the extracted material is 8-9. The hydrolysis procedure rids the oligomers of their terminal groups and converts some of the methyl ester groups to acid, greatly sim-plifying the mass spectrum. This appears to be the first direct measurement of “surfactants” produced in situ from monomer and persulfate initiator. © 1995 John Wiley & Sons, Inc.
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  • 8
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 643-648 
    ISSN: 0887-624X
    Keywords: free radical polymerization: kinetics of, catalytic inhibition in, catalytic chain transfer in ; cobaloxime ; methylmethacrylate ; methacrylamide ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Free radical polymerizations of methyl methacrylate and methacrylamide in DMF solution were found to be catalytically inhibited by the addition of the boron fluoride derivative of cobaloxime to the system. The nature of this inhibition is examined and equations which describe the kinetics of these catalytically inhibited polymerizations are developed. Using these equations estimates of the inhibition constants (Cz) of 7.23 × 102 and 2.27 × 102 were estimated for methacrylamide and methyl methacrylate, respectively.
    Additional Material: 5 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 2211-2216 
    ISSN: 0887-624X
    Keywords: emulsion polymerization ; core-shell ; redox ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Core-shell polymer composites made by two-stage emulsion polymerizations are useful in many applications. In systems involving a hydrophilic/hydrophobic polymer pair, a core-shell arrangement is thermodynamically unfavorable and may be difficult to achieve. To counteract the thermodynamic forces in such a system, the mobility of the phases can be reduced to such an extent that a core-shell morphology is achieved. This was accomplished in a PMMA/PS two-stage system by lowering the second-stage polymerization temperature to room temperature using a redox initiator. At this relatively low temperature, a core-shell morphology was obtained even when the second-stage was carried out as a batch polymerization. © 1992 John Wiley & Sons, Inc.
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  • 10
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 24 (1986), S. 2191-2198 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Free radical chain transfer constants have been measured by copolymerizing styrene and butyl acrylate in emulsion at 60°C. Some improvements to this experimental technique are reported and estimates are given of the sensitivity of the calculated values to experimental uncertainties. Monomer chain transfer constants were found to be 1.2 × 10-4 (styrene) and 2.5 × 10-4 (butyl acrylate). The sum of the cross-transfer constants is 2.7 × 10-4. The activation energy for chain transfer to styrene monomer is found to be 24 Kcal/mol in the 44°-60°C range.
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