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71.
72.
Grant T. D. Shouldice Phillip Y. Choi Bryan E. Koene Linda F. Nazar Alfred Rudin 《Journal of polymer science. Part A, Polymer chemistry》1995,33(9):1409-1417
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. 相似文献
73.
氧化-还原低温引发甲基丙烯酸甲酯/丙烯酸丁酯超浓乳液聚合研究 总被引:10,自引:0,他引:10
以乳化剂十二烷基硫酸钠 (SDS)和共乳化剂十六烷醇 (HD)作为复合乳化体系 ,过氧化二苯甲酰(BPO)和N ,N 二甲基苯胺 (DMA)作为氧化还原引发体系 ,甲基丙烯酸甲酯 丙烯酸丁酯 (MMA BA)作为混合单体 ,制备了分散相占 83 %以上的稳定的超浓乳液 ,然后在低温下引发聚合 .探讨了引发剂浓度、氧化剂与还原剂的摩尔比、乳化剂的浓度、液膜增强剂的种类、聚合温度等因素对聚合稳定性和聚合速率的影响 ,测定并计算得到了聚合速率的公式 ;用激光散射粒度分布仪测定了聚合物乳胶粒子的大小及粒径分布 ,用透射电子显微镜观察了聚合物乳胶粒的形态 ,讨论了乳化剂浓度、聚合温度等对乳胶粒形态、大小的影响 相似文献
74.
M. R. Castellar M. A. Taipa J. M. S. Cabral 《Applied biochemistry and biotechnology》1997,61(3):299-314
A kinetic study ofChromobacterium viscosum lipase was undertaken, and compared withPseudomonas glumae lipase. Optimum operation conditions were pH 9.0 and 50°C for both enzymes. A substrate specificity study was also developed. Both enzymes showed higher activity on triglycerides with a long chain of fatty acid; the specific activity was always higher for C.viscosum lipase. Stability of both enzymes in aqueous medium at 60°C and pH 9.0 was evaluated. C.viscosum lipase was three times more stable than P.glumae lipase, with at 1/2 value of 0.75 h. In addition, the activity of C.viscosum lipase with substrate concentration was studied with a triolein emulsion. A dependence of the intrinsic characteristics of the emulsion was observed. Therefore, stability ofC. viscosum lipase B with reaction products was assayed in a micellar system. Acid products reduced the specific activity of the enzyme. Glycerol and high buffer concentration were stabilizers of enzyme deactivation. Finally, substrate specificity ofC. viscosum lipase B in a micellar system was developed with tributyrin, tricaprylin, and triolein. Only tributyrin showed an apparent Michaelis-Menten kinetic with Vmax app = 958 U/mg and Kma app = 75.5 mM. Tricaprylin and triolein showed diffusion limitations at low substrate concentration and substrate inhibition at high substrate concentration. Diffusion parameters were calculated for both these substrates. Mass transfer coefficients (k1) were 0.314 Å/min and 1.53 Å/min for tricaprylin and triolein, respectively. Effectiveness factors (η) were 0.536 and 0.768 for tricaprylin and triolein, respectively. 相似文献
75.
Preben C. Mrk John Ugelstad Jan Ole Aasen 《Journal of polymer science. Part A, Polymer chemistry》1995,33(11):1759-1765
Expressions for calculating the stationary state distribution of radicals in compartmentalized systems with a constant number of reaction loci containing an oil-soluble initiator are given. Besides pairwise formation of radicals in the particles, desorption and reabsorption, water phase termination, solubility of the initiator in the aqueous phase, and the possibility of formation of a single radical species are taken into consideration. The calculation is based on a probabilistic analysis leading to a third-order recurrence relation solved using confluent, hypergeometric Kummer functions. Some calculated curves illustrating the de-pendence of the average number of radicals per particle on various relevant parameters are included. © 1995 John Wiley & Sons, Inc. 相似文献
76.
The effects of concentrations of surfactant (sodium lauryl sulfate [SLS]) and initiator (sodium persulfate [SPS]) on the polymerization of homogenized styrene emulsions, stabilized by SLS/lauryl methacrylate (LMA) or SLS/stearyl methacrylate (SMA), were studied. The rate of polymerization increases with increasing [SLS] or [SPS]. In addition to monomer droplet nucleation, the formation of particle nuclei in the aqueous phase (homogeneous nucleation) plays a crucial role in the polymerization kinetics. In comparison with the LMA containing polymerization system, monomer droplet nucleation becomes more important when the more hydrophobic SMA was used as the costabilizer. Furthermore, the degree of homogeneous nucleation increases with increasing [SPS]. 相似文献
77.
Jung Kwon Oh Jun Wu Mitchell A. Winnik Gary P. Craun Jude Rademacher Rajeev Farwaha 《Journal of polymer science. Part A, Polymer chemistry》2002,40(17):3001-3011
We describe the synthesis and characterization of three new polymerizable benzophenone derivatives [2‐acryloxy‐5‐methyl benzophenone ( 8 ), 4′‐dimethylamino‐2‐acryloxy‐5‐methyl benzophenone ( 9 ), and 4′‐dimethylamino‐2‐(β‐acryloxyethyl)oxy‐5‐methyl benzophenone ( 10 )]. We show that these monomers can successfully be incorporated into vinyl acetate (VAc) copolymer latex particles. These particles were prepared by semicontinuous emulsion polymerization and mini‐emulsion polymerization of VAc with butylacrylate (BA) for VAc/BA = 4/1 by weight. The two monomers 9 and 10 bearing the 4′‐dimethylamino group satisfy the important spectroscopic criteria required of a dye to serve as an acceptor chromophore for nonradiative energy transfer from phenanthrene (Phe) as the donor. Their UV absorption spectra suggest significant overlap with the emission spectrum of Phe, which can be incorporated into P(VAc‐co‐BA) latex through copolymerization with 9‐acryloxymethyl Phe ( 2 ). In addition, these chromophores provide a window in their absorption spectra for excitation of the Phe chromophore at 300 nm. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3001–3011, 2002 相似文献
78.
离聚体水基微乳液化的研究——聚苯乙烯离聚体微乳化过程相反转的表征 总被引:7,自引:0,他引:7
以乙酰磺酸为磺化剂制备磺化度为3~15mol%的磺化聚苯乙烯(SPS)并中和成盐.在一定的温度和搅拌速率下,加水将SPS乳化成水包油的稳定水基微乳液.用乳化过程中体系电导率和粘度的变化表征了乳化相反转过程.研究了溶剂的极性和离子含量对聚苯乙烯离聚体溶液可乳化性和乳化过程及乳液稳定性的影响. 相似文献
79.
80.
硅氧烷乳液聚合过程中大颗粒形成机理研究:Ⅰ.阳离子型乳液的耐电解质… 总被引:5,自引:1,他引:5
探讨了二甲基聚硅氧烷阳离子型乳液耐电解质稳定性的影响因素。结果表明,加入少量的非离子型表面活性剂与阳离子型乳化剂并用进行乳液聚合,可以保护乳液粒子,防止由于电解质引的乳液粒子的相互凝聚而形成大颗粒。 相似文献