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11.
Thomas Pautzsch Elisabeth Klemm 《Journal of polymer science. Part A, Polymer chemistry》2004,42(12):2911-2919
Poly{bis(4,4′‐tert‐butyl‐2,2′‐bipyridine)–(2,2′‐bipyridine‐5,5′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3a ), poly{bis(4,4′‐tert‐butyl‐2,2′‐bipyridine)–(2,2′‐bipyridine‐4,4′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3b ), and poly{bis(2,2′‐bipyridine)–(2,2′‐bipyridine‐5,5′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3c ) were synthesized by the Suzuki coupling reaction. The alternating structure of the copolymers was confirmed by 1H and 13C NMR and elemental analysis. The polymers showed, by ultraviolet–visible, the π–π* absorption of the polymer backbone (320–380 nm) and at a lower energy attributed to the d–π* metal‐to‐ligand charge‐transfer absorption (450 nm for linear 3a and 480 nm for angular 3b ). The polymers were characterized by a monomodal molecular weight distribution. The degree of polymerization was approximately 8 for polymer 3b and 28 for polymer 3d . © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2911–2919, 2004 相似文献
12.
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
13.
Dong Il Han Hoe Jin Hah Hong-Woo Park Sang Man Koo 《Journal of Sol-Gel Science and Technology》2004,32(1-3):47-51
Composite silica particles were synthesized by a two-step (acid-base) process in an aqueous solution with a mixture of organoalkoxysilane monomers. The two-step process separates the hydrolysis and condensation procedures to easily control condensation rate. In this study, the silane monomers used were phenyltrimethoxysilane (PTMS), vinyltrimethoxysilane (VTMS), methyltrimethoxysilane (MTMS), and tetraethyl-orthosilicate (TEOS). The physical properties of the resultant composite particles were investigated with the change in the molar ratio of monomers. The size of the particles increased with increasing the molar ratio of RaSi(OR)3/RbSi(OR)3 or RaSi(OR)3/TEOS (Ra: phenyl; Rb: vinyl, methyl). 相似文献
14.
Fukuji Higashi Kaori Kira 《Journal of polymer science. Part A, Polymer chemistry》2004,42(11):2725-2733
The solution polyesterification of dicarboxylic acids in pyridine, the activated intermediates of which were difficult to dissolve in tosyl chloride/dimethylformamide/pyridine, was investigated in the presence of lithium chloride. The solubility of the activated dicarboxylic acids was largely improved by the presence of the salt, and the polycondensation with bisphenols was greatly facilitated. The salt was more effectively added to a pyridine solution of dicarboxylic acids than to the activated dicarboxylic acids in pyridine. The favorable additive effect on the improved solubility was attributed to a lowered degree of association of the activated dicarboxylic acids, which led to distributions of the resulting oligomers from bisphenols at an earlier stage closer to the theoretical ones and yielded better polycondensation results. The reaction, which proceeded through favorable distributions of the co‐oligomers, produced copolymers of higher inherent viscosities and slightly block sequence distributions determined by NMR. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2725–2733, 2004 相似文献
15.
H. William Bosch Sre
o D. kapin Egon Matijevi 《Colloids and surfaces. A, Physicochemical and engineering aspects》2004,250(1-3):43-50
Controlled precipitation of the diagnostic imaging agent ethyl 3,5-di(acetylamino)-2,4,6-triiodobenzoate has been used to produce fine particles of various sizes, morphologies, and degrees of crystallinity, which depended on experimental conditions. In addition, two distinct polymorphic forms of the drug have been fully characterized by single crystal X-ray diffraction studies, and evidence for a third polymorph was also observed. Some of the so prepared dry particles were coated with a thin layer of silica. 相似文献
16.
Rodrigo París José Luis de la Fuente 《Journal of polymer science. Part A, Polymer chemistry》2007,45(16):3538-3549
Different diblock copolymers constituted by one segment of a monomer supporting a reactive functional group, like allyl methacrylate (AMA), were synthesized by atom transfer radical polymerization (ATRP). Bromo‐terminated polymers, like polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(butyl acrylate) (PBA) were employed as macroinitiators to form the other blocks. Copolymerizations were carried out using copper chloride with N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) as the catalyst system in benzonitrile solution at 70 °C. At the early stage, the ATRP copolymerizations yielded well‐defined linear block copolymers. However, with the polymerization progress a change in the macromolecular architecture takes place due to the secondary reactions caused by the allylic groups, passing to a branched and/or star‐shaped structure until finally yielding gel at monomer conversion around 40% or higher. The block copolymers were characterized by means of size exclusion chromatography (SEC), 1H NMR spectroscopy, and differential scanning calorimetry (DSC). In addition, one of these copolymers, specifically P(BA‐b‐AMA), was satisfactorily modified through osmylation reaction to obtain the subsequent amphiphilic diblock copolymer of P(BA‐b‐DHPMA), where DHPMA is 2,3‐dihydroxypropyl methacrylate; demonstrating the feasibility of side‐chain modification of the functional obtained copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3538–3549, 2007 相似文献
17.
Wenbing Hu Alexander Buzin Jar‐Shyong Lin Bernhard Wunderlich 《Journal of Polymer Science.Polymer Physics》2003,41(4):403-417
The annealing at 373 K of ultrastrong, gel‐spun polyethylene (PE) has been studied. At this temperature, the fibers show no significant shrinkage. Still, a significant decrease in the mechanical properties is observed. The fibers have been analyzed with differential scanning calorimetry (DSC), temperature‐modulated differential scanning calorimetry (TMDSC), atomic force microscopy (AFM), and small‐angle X‐ray scattering (SAXS). During the annealing, the glass transition of the intermediate phase is exceeded, as shown by DSC. When split for structure analysis by AFM, the annealed fibers undergo plastic deformation around the base fibrils instead of brittle fracture. The quasi‐isothermal TMDSC experiments are compared to the minor structural changes seen with SAXS and AFM. The loss of performance of the PE fibers at 373 K is suggested to be caused by the oriented intermediate phase, and not by major changes in the structure or morphology. The overall metastable, semicrystalline structure is shown by TMDSC to posses local regions that can melt reversibly. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 403–417, 2003 相似文献
18.
Whereas glucose oxidase and related proteins are encapsulated readily in silica sol–gels, α-hydroxy enzymes such as lactate
oxidase (LOx), are reported to be damaged by electrostatic interaction with these matrices. Based on a previous report, poly(ethyleneimine),
PEI, was evaluated as a protecting compound under conditions suited to analytical measurements. With LOx and PEI co-encapsulated
in a silica sol–gel, the enzyme retained 62% of its initial activity after 20 days. In the absence of PEI, activity was lost
during the processing. Batch analytical measurements with enzyme-doped sol–gel yielded a linear response over the range 0.5–2.0 mM
lactate and a detection limit of 0.03 mM lactate. Both simple incorporation of LOx in a silica sol–gel and an alternative
protection method, blocking the ion-exchange sites on silica with La(III), failed. These negative results supported the hypothesis
that the efficacy of PEI was related to its formation of a protective sheath around the enzyme.
Author for correspondence. E-mail: coxja@muohio.edu
Received July 29, 2002; accepted December 15, 2002
Published online May 19, 2003 相似文献
19.
In this paper, we report the conducting and electrochemical properties of a homogeneous V2O5-SiO2 xerogel composite obtained from the simultaneous polymerization in both inorganic components (Si-O and V-O based polymers) forming an interpenetrating polymer network, where a mutual “solubility” due to cross-links and entanglements was observed. The presence of V2O5 inside the silica matrix has a strong effect on electrical conductivity; measurements showed room temperature conductivity almost 1000 times higher than what is found in the literature. In addition, the electrochemical behavior is quite similar to that found in V2O5 xerogel. Moreover, the effects of thermal treatment on the conducting and electrochemical properties were investigated. It was found that both properties were improved with no significant effect on V2O5 xerogel layered structure. 相似文献
20.
Hydrogels of N‐vinylimidazole (VI) and sodium styrenesulfonate (SSS) were synthesized in aqueous solution by radical crosslinking copolymerization with N,N′‐methylene‐bis(acrylamide) as crosslinker. Swelling in several saline solutions was measured for hydrogel samples synthesized with different comonomer concentrations (CT = 10, 25, or 40%) and with SSS mole fractions covering a broad range (fSSS = 0–0.7), while the crosslinker ratio was 2 wt % in all cases. The degree of swelling in aqueous solution with a specific ionic strength (μ), plotted versus the SSS composition of the feed, shows a minimum for any set of samples synthesized with a fixed CT. The dependence of swelling on μ shows both polyelectrolyte (fSSS beyond the minimum) and antipolyelectrolyte behaviors (in the low fSSS limit). It was found that the nonGaussian factor of the crosslinking density and the polymer‐solvent interaction parameter increase with fSSS for any CT. Moreover, in the low fSSS limit, the osmotic swelling pressure is governed not only by the ionic contribution, but also by the polymer‐solvent mixing and, the concentration of mobile counterions inside the gel is not proportional to the net fixed charge but to the addition of cationic and anionic side groups, what discards the formation of ionic pairs. The antipolyelectrolyte effect is interpreted as due to the increasing protonation of VI as μ goes up. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1683–1693, 2007 相似文献