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  • 11
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 29 (1991), S. 857-867 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Monodisperse microscopic poly (methyl methacrylate)/polystyrene composite particles of 1-10 μm diameter were prepared by seeded emulsion polymerization of styrene in poly (methyl methacrylate) seed particles which were initially prepared by dispersion polymerization. The resulting composite particles were characterized by transmission and scanning electron microscopy. The unique morphology of the composite particles comprised three types of polystyrene domains embedded in a continuous poly (methyl methacrylate) matrix: the dispersed “internal” domains in the interior, the interconnected “subsurface” domains that from a crust beneath the surface, and the separated “surface” domains at the surface. In addition to thermodynamics and kinetics, the phase separation in composite particles is affected by polymerization mechanism. The complicated particle morphology found is attributed to the coexistence of bulk polymerization and emulsion polymerization (radical absorption and desorption) mechanisms. An explanation of the formation of the observed morphology is proposed. With varying poly (methyl methacrylate)/styrene ratio, the internal viscosity and the competition between the two polymerization mechanisms resulted in a series of interesting morphologies.
    Additional Material: 12 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 30 (1992), S. 2619-2629 
    ISSN: 0887-624X
    Keywords: emulsion polymerization, vinyl acetate ; emulsion polymerization, polymerizable surfactant ; emulsion polymerization, kinetics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A polymerizable surfactant, sodium dodecyl allyl sulfosuccinate (TREM LF-40; Henkel) and its nonpolymerizable counterpart were used in comparative studies of the emulsion polymerization of vinyl acetate. The conversion-time behavior differed for the two surfactants; the TREM LF-40 showed a decrease in the polymerization rate with increasing concentration while its hydrogenated derivative showed the opposite behavior, the rate increasing with increasing surfactant. Particle size analysis revealed a decreasing particle size with increasing surfactant concentration for both series of reactions. An explanation for the seemingly ambiguous results obtained for the polymerizable surfactant was sought by examining the reactivity of its vinyl group in copolymerization with vinyl acetate and its allylic group in a chain transfer reaction. The results suggest that both the copolymerization and chain transfer reactions can lead to the observed reduction in polymerization rate with increasing TREM LF-40 concentration. © 1992 John Wiley & Sons, Inc.
    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 25 (1987), S. 2595-2603 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of poly(styrene)/poly(styrene-co-acrylonitrile) core-shell latexes were synthesized by seeded emulsion polymerization. The dried latex was dissolved in toluene and then cast on the surface of water to form a very thin film (60-90 nm). Phase separation in the thin film was studied by transmission electron microscopy (TEM). Electron micrographs of these thin films yielded fine structure and interesting morphology that was unattainable by ultramicrotoming of the corresponding compression-molded specimens. Glass transition temperatures and percent grafted polystyrene were correlated with the TEM results. As grafting increases, mixing of the two phases improves, with the resulting Tg value being between the two Tg's of poly(styrene) and poly(styrene-co-acrylonitrile).
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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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.
    Type of Medium: Electronic Resource
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  • 15
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1501-1514 
    ISSN: 0887-6266
    Keywords: multicomponent ; latex ; interpenetrating polymer networks ; IPN ; core/shell ; damping ; loss area ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The integrals of the linear loss shear modulus vs. temperature (loss area, LA) and linear tan δ vs. temperature (tan δ area, TA) were characterized for various core/shell latex particles with synthetic rubber, poly(butadiene-stat-styrene) [P (Bd/S), 90/10], and interpenetrating polymer networks (IPN) as the cores. The IPN cores were composed of P(Bd/S) (Tg ≃ - 70°C) and an acrylate based copolymer (Tg around 10°C) for potential impact and damping improvement in thermoplastics. Poly(styrene-stat-acrylonitrile) (SAN, 72/28) was the shell polymer for all these polymers. Under the same loading, for both toughening and damping controls, among the IPN core/shell, blend of separate core/shell, and multilayered core/shell polymers, the IPN core/shell polymers were the best dampers. However, the other core/shell polymers also showed higher LA values than P(Bd/S)/SAN core/shell polymer. A comparison of LA values via a group contribution analysis method was made, the effect of particle morphology and phase continuity on damping being studied. Inverted core/shell latex particles (glassy polymer SAN was synthesized first) showed much higher LA and TA values than normal core/shell ones (rubbery polymer was synthesized first). Models for maximum LA and TA behavior are proposed. The damping property was essentially controlled by the phase miscibility and morphology of the core/shell latex particles. The LA values for each peak in these multiphase materials provided some indication of the several fractional phase volumes. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1501-1514, 1997
    Additional Material: 9 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 41 (1990), S. 2463-2477 
    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 80/20 (w/w) azeotropic styrene/acrylonitrile mixture was copolymerized at 35, 50, and 70°C in crosslinked polybutadiene seed latexes of varying particle size (range 113-242 nm) using the t-butyl or cumene hydroperoxide/sodium formaldehyde sulfoxylate dihydrate/EDTA-chelated Fe+2 redox initiator. Other initiators used for comparison were: (1) ammonium persulfate at 70°C; (2) ammonium persulfate/sodium bisulfite redox initiator at 35 and 50°C; (3) oil-soluble, 2,2'-azobis(2,4-dimethylvaleronitrile) at 50°C. The following polymerization parameters were varied systematically: (1) polybutadiene seed latex particle size; (2) monomer/polymer swelling ratio; (3) polymerization temperature; (4) type and concentration of initiator; and (5) mode (and duration) of initiator addition. The following parameters were determined: (1) polymer yield (final conversion); (2) variation of conversion with time; (3) morphology of the latex particles; (4) amount of coagulum; and (5) fraction of styrene/acrylonitrile monomer mixture grafted to the polybutadiene seed latex (defined here as grafting efficiency). For polymerizations using the t-butyl or cumene hydroperoxide/sodium formaldehyde sulfoxylate dihydrate/EDTA-chelated Fe+2 redox initiator, the rates of polymerization were faster, the grafting efficiencies were greater, and the amounts of coagulum were greater at 70°C than at 50 or 35°C. The rates of polymerization were decreased by decreasing the concentration of redox initiator or adding it incrementally. A 1.00/1.00/0.08 (w/w) t-butyl or cumene hydroperoxide/sodium formaldehyde sulfoxylate dihydrate/EDTA-chelated Fe+2 ratio gave reasonable polymerization rates at 35 and 50°C, and a 0.48/1.00/0.07 ratio, at 70°C. The latexes were stabilized during polymerization with 3% (based on seed solids) nonionic Igepal CO-990 at 35°C, and 6% at 50 and 70°C. The grafting efficiency increased with decreasing particle size of the polybutadiene seed latex and decreasing monomer/polymer ratio. The rate of polymerization increased with decreasing monomer/polymer ratio. The monomer/polymer ratio also affected the morphology of the particles; higher values gave inclusions of poly(styrene-co-acrylonitrile) in the polybutadiene particles. There were no significant differences in polymerization kinetics or grafting efficiency between the t-butyl and cumene hydroperoxides.
    Additional Material: 6 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 58 (1995), S. 375-384 
    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: Core/shell structured latex particles with an interpenetrating polymer network (IPN) core(polymer A and polymer B) and glassy shell (polymer C) were synthesized by emulsion polymerization techniques. Polymer A was poly(butadiene-stat-styrene) (90/10) (P(Bd/S)). Polymer B was either poly(butyl acrylate-stat-methyl methacrylate) (60/40) or poly(butyl acrylate-stat-styrene) (60/40) prepared by a sequential IPN technique to form the cores. The glass transition temperatures, Tg, of polymer A and polymer B were around -70 and 10°C, respectively. The shell, polymer C, poly(styrene-stat-acrylonitrile) (72/28), was polymerized with grafting onto the IPN core by a semicontinuous process. The particle size and particle size distribution were measured by light-scattering, capillary hydrodynamic fractionation, and transmission electron microscopy. The glass transition temperatures were determined by differential scanning calorimetry. The polymer A (particle sizes between 200-270 nm) with different gel fractions was used to characterize the effect of gel fraction on IPN morphology. A core/shell type phase separation was observed for IPN particles when using a polymer A with 〉 90% gel fraction. A distribution of polymer B domains in polymer A was obtained when using polymer A with a 40% gel fraction. A good coverage of polymer C on the IPN core particles was obtained at a core/shell ratio of one to one. A broad glass transition range for the core/shell structured latex particles was observed. In article II of this series, these latex particles will be used to toughen such engineering thermoplastics as polycarbonates to understand the particular toughening theories of these polymers. © 1995 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
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  • 18
    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: Composition, molecular weight, and microstructure of the “shell” polymer in core-shell structured latex particles, designed for toughening polycarbonate matrix, should be controlled for enhanced miscibility between the shell polymer and the matrix. Various “shell polymer” systems based on styrene (St) and benzyl methacrylate (BM) were synthesized. Reactivity ratios were determined for (St) and (BM). Chain transfer efficiency studies revealed the susceptibility of styrene to transfer to a chain transfer agent. Benzyl methacrylate was found to have steric and stability factors hindering its tendency to chain transfer with various chain transfer agent. Miscibility tests between P(St/BM) and polycarbonate (PC) indicated different degrees of miscibility, depending upon polymerization conditions. Factors other than molecular weight, such as branching and crosslinking, were found to play a role in the miscibility. Monodisperse poly(n-butyl acrylate) (PBA) seed latex particles of variable degree of crosslinking and particle size were successfully synthesized by batch emulsion polymerization. © 1995 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 58 (1995), S. 265-269 
    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: Significant adsorption of polystyrene-poly(ethylene oxide) (PS-PEO) diblock copolymers onto PS latex particles in an aqueous dispersion is accomplished through suppression of micelle formation by adding tetrahydrofuran (THF) as a cosolvent. We add THF, a good solvent for the micelle core, to weaken the micelle and allow free chains for adsorption to the colloidal particles. Choosing a PS colloidal particle as the adsorption substrate (thus the adsorbed PS block can fully wet the subsurface), we eliminate the complications which arise from micelle formation on the colloidal surface. Since the PS particles swell in the mixed solvent, the adsorbed PS block may penetrate into the swollen latex core, which is favored for entropic reasons. A subsequent water quench of the system to a low THF solution shrinks the PS particle to its original size while retaining most of the adsorbed polymers. The adsorbed chains cannot be removed by adding surfactants or raising temperature to 90°C, indicating that the adsorbed layer is tightly attached to the surface due to kinetic hinderance of the chains in a confined environment. Neutron scattering experiments is being carried out to settle whether the PS penetrates the PS particle. © 1995 John Wiley & Sons, Inc.
    Additional Material: 3 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. 891-900 
    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: Bulk and emulsion copolymerizations of an ω-unsaturated poly(methyl methacrylate) (PMMA) macromonomer with n-butyl acrylate (n-BA) were investigated. The reactivity of PMMA macromonomer in bulk copolymerization with n-BA was found to be lower than that of methyl methacrylate monomer with n-BA. The incorporation of PMMA macromonomer into poly(butyl acrylate) (PBA) latex particles by miniemulsion copolymerization was proved by high performance liquid chromatography-silica adsorption spectroscopy. Dynamic mechanical studies showed that PMMA macromonomer was grafted to the PBA backbone, and the degree of grafting increased as the ratio of PMMA macromonomer to n-BA increased. Microphase separation of the PMMA macromonomer grafts was observed at higher ratio of macromonomer (higher or equal to 10% weight of macromonomer based on total polymer phase). The n-BA/PMMA macromonomer copolymer behaved completely differently from the physical blend of PBA and PMMA macromonomer particles of the same composition. © 1996 John Wiley & Sons, Inc.
    Additional Material: 12 Ill.
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