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991.
Unmodified and SiCl4-modified spherical zirconia-supported methylaluminoxane were used as cocatalyst for propylene polymerization as well as ethylene/1-hexene copolymerization in combined with Me2Si(η3-C13H8)(η1-NtBu)TiMe2 (1) at 0 °C. The modification with SiCl4 improved the catalytic activity. The improvement was clearer in ethylene/1-hexene copolymerization than in propylene polymerization. The number average molecular weight (Mn) of polypropylenes increased linearly against the polymerization time regardless the cocatalyst used to give polymers with narrow molecular weight distribution (Mw/Mn < 1.32), indicating the living nature of the catalytic systems. Thus, propagation rate constant (kp) and the number of active centers (C*) were evaluated from Mn and the number of polymer-chains. When the zirconia was modified with SiCl4, the kp value decreased and the C* increased. The latter effect was more significant to enhance the catalytic activity. 相似文献
992.
Andrea Frank Andreas Berkefeld Matthias Drexler Heiko M. Mller Thomas E. Exner 《International journal of quantum chemistry》2013,113(13):1787-1793
Neutral Ni(II) complexes have been shown to be highly valuable as robust and versatile catalysts in olefin polymerization. But they show reduced reactivity when the polar monomers methyl acrylate and vinyl acetate are incorporated. To get further insight into this behavior, NMR chemical shift calculations were performed on the system [(N,O) Ni (H) (PMe3)] 1 (N,O = ‐N,O‐{2,6‐(3,5‐(F3C)2C6H3)2C6H3) NC(H)‐3,5‐I2‐2‐O‐C6H2}). The chemical shifts show reasonable agreement with experiment but are also extremely influenced by geometrical features of the complex as well as the inserted substrate. The first prominent feature, the low‐field shift of the Ccarbonyl in the incorporated monomer, can only be reproduced when it is in close proximity to the Ni and in this way hinders the attack of a new monomer. Second, the almost 100 ppm difference in the chemical shift of the carbon of the two substrates directly bound to Ni can be reasoned by the different directionality of polarization as disclosed by natural bond orbital (NBO) analysis. © 2013 Wiley Periodicals, Inc. 相似文献
993.
11,11′-Dithiobis[1-(2-bromo-2-methylpropionyloxy)undecane], a conventional initiator for grafting polymers from gold surfaces, was synthesized in two steps from 11-mercapto-1-undecanol in 88–92% overall yield. Oxidative dimerization of 11-mercapto-1-undecanol with a catalytic amount of sodium iodide and 30% hydrogen peroxide in ethyl acetate proceeded in 96% yield. Esterification with 2-bromoisobutyryl bromide in dichloromethane was clean and almost quantitative (92% yield) with pyridine used as base, whereas triethylamine gave a messy reaction (64% yield). Alternatively, esterification with 2-bromo-2-methyl-propanoic acid in dichloromethane occurred readily under Steglich's conditions with N,N′-dicyclohexylcarbodiimide (DCC) and a catalytic amount of dimethylaminopyridine (DMAP; 88% yield). 相似文献
994.
An efficient method for the oxidation of alcohols is presented. The use of catalytic amounts of sodium chloride in combination with oxone allows the conversion primary aliphatic alcohols to symmetric esters. Secondary alcohols can be easily oxidized to ketones, and benzylic alcohols are converted to the corresponding aldehydes. The method is cost effective and enviromentally benign. 相似文献
995.
The reaction of 3-acylsubstituted 2H-1-benzo-pyran-2-ones 1, 5 and 11a-c with acid anhydrides in the presence of potassium fluoride (KF)/molecular sieves 4A gives the 4-(2-oxoalkyl)-2-oxochromans 2, 6 and 12a-c as the main products. Also the 3-carboxylic acid derivatives, such as esters and N,N-dialkylamides, of 2H-1-benzopyran-2-one (11d-g) react with isobutyric acid anhydride in the presence of KF/molecular sieves 4A to give the corresponding 2-oxochroman-4-acetic acid derivatives. 相似文献
996.
997.
Wei Chang Lijuan Liu Jin Zhang Qiwei Pan 《Journal of Dispersion Science and Technology》2013,34(5):639-642
A kind of emulsifier-free latex (FL) was successfully synthesized from styrene (St) and butyl acrylate (BA) with 2-acrylamido-2-methyl propane sulfonic acid (AMPS) as a reactive emulsifier. The particle size of latex particles, stability against electrolytes, minimum film forming temperature (MFT) and water contact angle (CA) were evaluated and compared with a conventional latex (CL). Test results show that FL has larger particle size, better stability against electrolytes and lower MFT value compared with CL; higher AMPS content leads to smaller particle size and smaller water CA. 相似文献
998.
María-Teresa Celis Luis H. Garcia-Rubio 《Journal of Dispersion Science and Technology》2013,34(1-3):293-299
In emulsion polymerization, the formation of particles has an important effect on the rate of reaction and on the final properties of the latex. To investigate particle nucleation mechanisms in emulsion polymerization it is necessary to establish the initial conditions of the emulsified system before the reaction takes place. This research reports on a technique to continuously monitor the droplet size distribution of liquid-liquid emulsions using spectroscopy. The on-line particle characterization methodology is based on an integrated sampling and dilution strategy combined with spectroscopy methods. It is shown that the sampling system integrated with a multiwavelength turbidity detector provides reliable estimates of droplet populations as function of the dispersed phase concentration in emulsions of saturated hydrocarbons. The results provide not only the groundwork necessary for the elucidation of particle nucleation during emulsion polymerization process but also suggests the potential of this combined technology to further our understanding of liquid-liquid emulsions. 相似文献
999.
Fu-Qiang Jin Jian-Chun Zhang Min Li Xin-Min Hao Hua Zhang 《Journal of Dispersion Science and Technology》2013,34(8):1148-1151
NaOH/poly(sodium acrylate) composites were prepared by in situ polymerization of acrylic acid with an overneutralization level by adding excess NaOH. The composites were studied by XRD, IR and 23Na MAS NMR spectroscopy. The results showed that the high neutralization degree (>100%) may lead to a complete polymerization. Both XRD and 23Na MAS NMR spectra did not show any peaks of phase-separated NaOH or Na2CO3 until the neutralization degree was up to 217.5%. It can be presumed that the aggregates of Na+ ions can contain approximately two Na+ units for every carboxyl group before the phase separation. 相似文献
1000.
Young-Sang Cho 《Journal of Dispersion Science and Technology》2013,34(9):1237-1246
In this study, monodisperse latex particles with specific surface functional groups were synthesized by emulsifier-free emulsion polymerization. Amidine or carboxylated polystyrene nanospheres with narrow size distribution were prepared by emulsion polymerization using AIBA (α,α′-zodiisobutyramidine dihydrochloride) as amine-containing initiator or acrylic acid as carboxyl-containing comonomer, respectively. Factors affecting the particle size and distribution were systemically studied by changing the amount of initiator or monomer, the polymerization temperature, and the stirring speed of emulsion polymerization reactor. Monodisperse polymethylmethacrylate beads were also synthesized by soapless emulsion polymerization using methacrylic acid or aminoethylmethacrylate hydrogen hydrochloride as comonomer for the surface functionalization of the particles. As applications of the latex beads, the polymeric particles were adopted as templating materials for the fabrication of macroporous titania film and meso-macroporous silica particles by colloidal templating method. 相似文献