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  • Polymer and Materials Science  (22)
  • Inorganic Chemistry  (4)
  • reaction calorimetry  (3)
  • NMR relaxation studies  (2)
  • [3H]Acetylcholine release  (2)
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Keywords
  • 11
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    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
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
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  • 12
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3827-3835 
    ISSN: 0887-624X
    Keywords: reaction calorimetry ; emulsion polymerization ; n-butyl acrylate ; nonionic surfactant ; Triton X-405 ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the emulsion polymerization of n-butyl acrylate, the nonionic surfactant Triton X-405 (octylphenoxy polyethoxy ethanol) partitions primarily into the aqueous phase leading to nucleation in the presence of micelles and unimodal final latex particle size distributions. Nucleation is accompanied by limited aggregation in the early stages of the reactions with particles being formed in some cases past 50% conversion depending on the experimental conditions. High values of the average number of radicals per particle (n̄ 〉 10) are observed during these reactions which explains a secondary increase in the heat of reaction. This increase was not observed when the initiator (K2S2O8) concentration was reduced from 6.4 to 0.6 mM or the temperature was decreased from 70°C to 60°C; contrary to what was expected, an inverse relationship was observed between the rate of polymerization and the final number of particles for these experiments. This was attributed to more extensive limited aggregation at the higher temperature and initiator concentration. Limited aggregation is thus shown to be an important mechanism in these polymerizations. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3827-3835, 1997
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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  • 13
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3837-3846 
    ISSN: 0887-624X
    Keywords: reaction calorimetry ; emulsion copolymerization ; styrene ; n-butyl acrylate ; nonionic surfactant ; Triton X-405 ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Emulsion copolymerizations of styrene and n-butyl acrylate were conducted at 70°C using varying amounts of Triton X-405 (octyl phenoxy polyethoxyethanol) as emulsifier. The kinetic behavior was found to vary widely depending on the emulsifier concentration. Unimodal particle size distributions were produced at the lowest (4.2 mM) and the highest levels (12.5 mM, 16.2 mM) of emulsifier while at intermediate levels (6.3 mM and 8.4 mM) bimodal distributions were produced; these were reflected in the reaction kinetics. These results were attributed to the surfactant partitioning behavior in the system which led to homogeneous/coagulative nucleation at the lowest level to homogeneous/coagulative nucleation followed by micellar nucleation at the intermediate levels to micellar nucleation at the highest levels. Although the added surfactant levels were all well above that required to exceed its CMC in the aqueous phase, the substantial partitioning into the oil phase lead to conditions well below the CMC of the portion of the surfactant present in the aqueous phase for the lowest and the intermediate levels of the Triton X-405. Consequences of this partitioning were seen in a semibatch reaction where all the surfactant was initially present in the aqueous phase; in this case, too many particle were nucleated leading to massive coagulation due to insufficient surfactant being available to stabilize the particles. © John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3837-3846, 1997
    Additional Material: 10 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 849-862 
    ISSN: 0887-624X
    Keywords: vinyl acetate ; emulsion polymerization of ; poly(vinyl alcohol) emulsifier ; poly(vinyl alcohol) ; grafting onto ; acetonitrile/water extraction ; water-soluble PVA ; water-insoluble PVA ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: During the emulsion polymerization of vinyl acetate (VAc) using poly(vinyl alcohol) (PVA) as stabilizer and potassium persulfate as initiator, the VAc reacts with PVA forming PVA-graft-PVAc. When the grafted polymer reaches a critical size it becomes water-insoluble and precipitates from the aqueous phase contributing to the formation of polymer particles. Since particle formation and therefore the properties of the final latex will depend on the degree of grafting, it is important to quantify and to characterize the grafted PVA. In this work, the quantitative separation and characterization of the grafted water-insoluble PVA was carried out by a two-step selective solubilization of the PVAc latex, first with acetonitrile to separate PVAc homopolymer, followed by water to separate the water-soluble PVA from the remaining acetonitrile-insoluble material. After the separation, the water-soluble and water-insoluble PVA were characterized by Fourier Transform Infrared (FTIR) spectroscopy and 1H and 13C nuclear magnetic resonance (NMR) analyses, from which the details of the PVA-graft-PVAc structure were obtained. © 1996 John Wiley & Sons, Inc.
    Additional Material: 19 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 30 (1992), S. 787-789 
    ISSN: 0887-6266
    Keywords: latex particles, SANS study of internal morphology of ; chain segment distribution of high MW polymer in small sphere ; polystyrene in latex spheres, segmental distribution of ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 16
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 30 (1992), S. 1311-1319 
    ISSN: 0887-6266
    Keywords: polystyrene, chain scission in fracture of ; fracture of glassy polymers, energy consuming micromechanisms ; chain scission mechanism in fracture of polystyrene ; glassy polymers, chain scission and fracture of ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The number of chain scissions per unit area that occur during the fracture of partially annealed latex films from Mn ≃ 180,000 g/mol polystyrene particles of about 275 Å radius were measured and correlated to annealing times. A curve with four regimes was found. At short annealing times the curve is nearly flat, in what is called the chain pull-out regime. In the second regime, the number of chains broken per unit area increases with a 0.8 power of annealing time as entanglement of the diffusing polymer chains increases in neighboring host particles. This is in good agreement with Wool's theory which predicts a 0.75 power dependence. Then, after reaching a peak, the number of scissions decreases in the third regime, indicating a change in fracture mechanism. The number of chain scissions increases again in the fourth regime, as final healing of the film interface takes place. Fracture surface analysis reveals a rough surface for short annealing times and a smooth surface for longer annealing times. The number of polymer chain scissions per unit area of fracture surface showed no dependence on initial molecular weights for t ≫ τr where t and τr are annealing and relaxation times, respectively. The number of chain bridges crossing a unit area of interface was suggested as the basic molecular property. © 1992 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 40 (1990), S. 1005-1021 
    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 appearance of pseudo-steady states in semicontinuous emulsion copolymerization is studied. Different correlations between the monomer feed rate and the polymerization reaction rate proposed in the literature for homopolymerization systems can be derived from a unified view as presented in this work. The theoretical analysis for copolymerization systems predicts that the individual consumption rates of both monomers involved assume a constant value if the monomer addition rates are kept constant. Different cases for either fixed radical concentration or seeded polymerization with water-soluble or sparingly water-soluble monomers are considered. The assumptions and results of the analysis are tested against experimental data from the seeded copolymerization of vinyl acetate/n-butyl acrylate.
    Additional Material: 6 Ill.
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  • 18
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 27 (1989), S. 1649-1662 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The development of supermolecular structure in polystyrene latex particles was investigated by small-angle neutron scattering (SANS). Seed latexes of deuterated polystyrene were swollen with an equal mole-% of protonated styrene monomer, equilibrated, and polymerized to complete conversion. The scattering patterns reflect the extent of supermolecular structure development inside the particle. The data were analyzed by separating the Debye single-chain and spherical scattering form factors. The extent of segregation was found to depend on the relative size of the chains compared with that of the particle, going through a maximum at the ratio Mw/Dw2 of about 0.1, where Dw represents the weight-average diameter of the latex particle. When the chain dimensions are relatively very small, uniform molecular mixing is obtained. The best model for the segregated system is a graduated core-shell supermolecular structure.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 19
    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: Poly(divinylbenzene)/poly(n-butyl acrylate) core/shell latexes were investigated using solid-state 13C-NMR. The (H)T1ρ relaxation time was found to be substantially affected by many of the seeded emulsion polymerization parameters, such as the core/shell ratio, the mode of addition of the second-stage monomer, the addition rate of the second-stage monomer, and the level of conversion of the seed latex at the time of addition of the second-stage monomer. The existence of an interphase region between the core and shell polymers was detected. Maximum interphase region thickness was achieved when the butyl acrylate was added under starved conditions. The thickness of this interphase layer was calculated to be 5-7 nm based on a model proposed by McBriety.1 Solid-state NMR was found to be an excellent spectroscopic technique to probe the interphase region in core/shell latexes. © 1995 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
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  • 20
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 61 (1996), S. 911-921 
    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: Dimethyl meta-isopropenyl benzyl isocyanate (TMI®) is a bifunctional monomer possessing a double bond and an isocyanate group. Emulsion terpolymerization of TMI with the acrylic monomers, methyl methacrylate and n-butyl acrylate, was studied. Polymerizations were carried out at 40°C using a redox initiator system in order to minimize the extent of hydrolysis of the isocyanate in the aqueous emulsion environment. The kinetics of the polymerization reaction were investigated. The polymerization rate was found to decrease with increasing TMI concentration. The effects of several preparative variables such as the monomer, surfactant, and initiator concentration on the polymerization kinetics was studied. Several semicontinuous polymerization processes were developed in order to enhance the incorporation of TMI at appreciable rates. These processes also allow us to control the polymer composition, latex particle size, and the locus of isocyanate groups in the latex particle. Process variables such as the mode of initiator addition (batch versus semicontinuous) were found to greatly influence the polymerization behavior. © 1996 John Wiley & Sons, Inc.
    Additional Material: 18 Ill.
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