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981.
7‐Octenyldimethylphenylsilane was copolymerized with ethylene via Et(Ind)2ZrCl2 methylaluminoxane catalyst system without loss of catalyst activity or decrease in molar mass. The comonomer contents in the polymer samples were at a level of 0.15–1.0 mol % and the reactive phenylsilane groups were posttreated to different alcoxy‐ and halosilane groups, for example, Si? F, Si? Cl, Si? OCH3, and Si? OCH2CH3. The posttreatment reactions had no major effect on the molar masses or on the thermal properties (measured with differential scanning calorimetry) of the copolymers. The reaction pathways were nearly independent of the comonomer contents and the reactions reached 70–100% conversions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1461–1467, 2004 相似文献
982.
Jeremy R. Lizotte Sara G. Anderson Timothy E. Long 《Journal of polymer science. Part A, Polymer chemistry》2004,42(7):1547-1556
A novel dinitroxide mediating agent that was suitable for stable free‐radical polymerization was synthesized and used in the block copolymerization of styrene and t‐butyl styrene. Quantitative yields of a novel dinitroxide based on 1,6‐hexamethylene diisocyanate and 4‐hydroxy‐2,2,6,6‐tetramethyl‐1‐piperidinyloxy were obtained. Various experimental parameters, including the nitroxide‐to‐initiator molar ratio, were examined, and it was determined that the polymerization was most controlled under conditions similar to those of conventional 2,2,6,6‐tetramethyl‐1‐piperidinyloxy‐mediated stable free‐radical polymerization. Moreover, the dinitroxide mediator proved to be a viable route for the facile two‐step synthesis of triblock copolymers of styrene and t‐butyl styrene. However, the dinitroxide mediation process resulted in a higher than expected level of nitroxide decomposition, which resulted in polymers possessing a terminal alkoxyamine and an adjacent hydroxylamine rather than a preferred internal bisalkoxyamine. This decomposition resulted in the formation of diblock copolymer species during the triblock copolymer synthesis. Gel permeation chromatography was used to monitor the chain‐end decomposition kinetics, and the determined observed rate constant (5.89 × 10?5 s?1) for decomposition agreed well with previous studies for other dinitroxide mediating agents. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1547–1556, 2004 相似文献
983.
Do W. Lee Eun Y. Seo Sung I. Cho Chae S. Yi 《Journal of polymer science. Part A, Polymer chemistry》2004,42(11):2747-2755
Pyridine‐2‐carboximidates [methyl ( 1a ), ethyl ( 1b ), isopropyl ( 1c ), cyclopentyl ( 1d ), cyclohexyl ( 1e ), n‐octyl ( 1f ), and benzyl ( 1g )] were prepared from the reaction of 2‐cyanopyridine with the corresponding alcohols. Cyclopentyl‐substituted 1d was found to be a highly effective ligand for copper‐catalyzed atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA). For example, the observed rate constant for a CuBr/ 1d catalytic system was found to be nearly twice as high as the cyclohexyl‐substituted CuBr/ 1e catalytic system [kobs = (1.19 vs 0.56) × 10?4 s?1). The effects of the solvents, temperature, catalyst/initiator, and solvent/monomer ratio on the ATRP of MMA were studied systematically for the CuBr/ 1d catalytic system. The optimum condition for the ATRP of MMA was found to be a 1:2:1:400 [CuBr]o/[ 1d ]o/[ethyl 2‐bromoisobutyrate]o/[MMA]o ratio at 60 °C in veratrole solution, which yielded well‐defined poly(MMA) with a narrow molecular weight distribution of 1.14. The catalytically active copper complex 2d was isolated from the reaction of CuBr with 1d . Narrow molecular weight distributions as low as 1.06 were achieved for the CuBr/ 1d catalytic system by employing 10% of the deactivator CuBr2. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2747–2755, 2004 相似文献
984.
Strain hardening of polycarbonate in the glassy state: Influence of temperature and molecular weight
L. E. Govaert T. A. Tervoort 《Journal of polymer science. Part A, Polymer chemistry》2004,42(11):2041-2049
This study is concerned with the temperature and molecular weight dependence of the strain-hardening behavior of polycarbonate. It is shown that the strain-hardening modulus reduces with increasing temperature and decreasing molecular weight. This result is interpreted in terms of temperature accelerated relaxation of the entanglement network. Moreover, it is shown that frozen-in orientations, induced by homogeneous deformations above the glass transition temperature, lead to anisotropic yield behavior that can be fully rationalized (and modelled) in terms of a superimposed stress contribution of the prestrained network. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2041–2049, 2004 相似文献
985.
Tin and titanium ferrocyanides were studied as adsorbents for alkali metal ions, viz., 134Cs and 22Na, which represent radioactive wastes. The ferrocyanides were prepared in granular form. The tin version contained 11.2% water, while the titanium version contained 17.7% water. The exchange capacities for Cs+ and Na+ in the hydrated tin version were about 1.5 and 0.7 meq/g, respectively, while those in the titanium version were 2.2 and 1.2 meq/g, respectively. Drying at 250°C decimated those capacities. The diffusional time constant of Cs+ at 25°C, determined via Fick's second law, was of order of magnitude 1 × 10–3 s–1, though there were minor differences due to particle size and the form of ferrocyanide. Similarly, the effective diffusivity was of order of magnitude 1 × 10–8 cm2/s. The titanium version responded slightly faster than the tin version. Likewise, equilibrium measurements in mixtures with sodium nitrate, potassium nitrate, or uranium oxide, showed that the titanium version exhibited significantly greater selectivity for Cs+ than did the tin version. Unfortunately, tests of complete elution of the Cs+ from the ferrocyanides were mostly disappointing. Work continues on that subject. 相似文献
986.
N. A. Hussein A. Shukri A. A. Tajuddin C. S. Chong 《Radiation Physics and Chemistry》2004,71(6):1077-1086
Osteoporosis is a bone condition that is caused mainly by the degradation of trabecular and cortical bone resulting in the decrease of bone strength and eventually leads to bone fracture. A low angle X-ray scattering (LAXS) system that uses mainly the coherent scattering process for the characterisation of materials was constructed to study such bone conditions. Several finger phantoms were fabricated to simulate bone of varying densities. The LAXS method was able to identify the changes in bone density quite well by comparing energy dispersive X-ray diffraction patterns as well as the angular patterns. Quantitative information can be extracted from such patterns that relate to bone loss. Signature patterns at low exposure times were produced in order to reduce the dose received with reasonable identification power but at slightly higher statistical errors compared with long exposure patterns. Use of other parameters to increase the sensitivity was attempted. 相似文献
987.
JPC – Journal of Planar Chromatography – Modern TLC - Flavonoid glycosides are much more polar than their aglycones and the two groups of compounds are difficult to separate by planar... 相似文献
988.
Alvaro Carrillo Ravi S. Kane 《Journal of polymer science. Part A, Polymer chemistry》2004,42(13):3352-3359
This article describes the formation and characterization of self‐assembled nanoparticles of controlled sizes based on amphiphilic block copolymers synthesized by ring‐opening metathesis polymerization. We synthesized a novel hydrophobic derivative of norbornene; this monomer could be polymerized using Grubbs' catalyst [Cl2Ru(CHPh)(PCy3)2] forming polymers of controlled molecular weight. We synthesized amphiphilic block copolymers of controlled composition and showed that they assemble into nanoparticles of controlled size. The nanoparticles were characterized using dynamic light scattering and transmission electron microscopy. Tuning the composition of the block copolymer enables the tuning of the diameters of the nanoparticles in the 30‐ to 80‐nm range. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3352–3359, 2004 相似文献
989.
Irada S. Isayeva Joseph P. Kennedy 《Journal of polymer science. Part A, Polymer chemistry》2004,42(17):4337-4352
This article concerns the synthesis and characterization of novel tricomponent amphiphilic membranes consisting of hydrophilic poly(ethylene glycol) (PEG) and hydrophobic polydimethylsiloxane (PDMS) segments cocrosslinked and reinforced by octasilane polyhedral oligomeric silsesquioxane (octasilane‐POSS) cages. Rapid and efficient network synthesis was effected by cocrosslinking diallyl‐telechelic PEG (A‐PEG‐A) and divinyl‐telechelic PDMS (V‐PDMS‐V) with pentamethylpentacyclosiloxane (D5H), using Karstedt's catalyst in conjunction with Et3N cocatalyst and water. Films were prepared by pouring charges in molds and crosslinking by heating at 60 °C for several hours. The films were characterized by sol fractions and equilibrium swelling both in hexane and water, extent of crosslinking, contact angle hysteresis, oxygen permeability, thermogravimetric analysis, and mechanical properties. The crosslinking of octasilane‐POSS achieved by the same catalyst system was studied in separate experiments. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4337–4352, 2004 相似文献
990.
Gottfried Mayer Vitali Vogel Bas G. G. Lohmeijer Jean‐Franois Gohy Jacomina A. Van Den Broek Winfried Haase Ulrich S. Schubert Dieter Schubert 《Journal of polymer science. Part A, Polymer chemistry》2004,42(17):4458-4465
Micelles prepared from amphiphilic block copolymers in which a poly(styrene) segment is connected to a poly(ethylene oxide) block via a bis‐(2,2′:6′,2″‐terpyridine‐ruthenium) complex have been intensely studied. In most cases, the micelle populations were found to be strongly heterogeneous in size because of massive micelle/micelle aggregation. In the study reported in this article we tried to improve the homogeneity of the micelle population. The variant preparation procedure developed, which is described here, was used to prepare two “protomer”‐type micelles: PS20‐[Ru]‐PEO70 and PS20‐[Ru]‐PEO375. The dropwise addition of water to a solution of the compounds in dimethylformamide was replaced by the controlled addition of water by a syringe pump. The resulting micelles were characterized by sedimentation velocity and sedimentation equilibrium analyses in an analytical ultracentrifuge and by transmission electron microscopy of negatively stained samples. Sedimentation analysis showed virtually unimodal size distributions, in contrast to the findings on micelles prepared previously. PS20‐[Ru]‐PEO70 micelles were found to have an average molar mass of 318,000 g/mol (corresponding to 53 protomers per micelle, which is distinctly less than after micelle preparation by the standard method) and an average hydrodynamic diameter (dh) of 18 nm. For PS20‐[Ru]‐PEO375 micelles, the corresponding values were M = 603,000 g/mol (31 protomers per micelle) and dh = 34 nm. The latter particles were found to be identical to the “equilibrium” micelles prepared in pure water. Both micelle types had a very narrow molar mass distribution but a much broader distribution of s values and thus of hydrodynamic diameters. This indicates a conformational heterogeneity that is stable on the time scale of sedimentation velocity analysis. The findings from electron microscopy were in disagreement with those from the sedimentation analysis both in average micelle diameter and in the width of the distributions, apparently because of imperfections in the staining procedure. The preparation procedure described also may be useful in micelle formation from other types of protomers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4458–4465, 2004 相似文献