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91.
The Brønsted acidity of the various Si(nAl) sites present in zeolites is evaluated from proton binding energy and LUMO energy calculated by the semiempirical MNDO quantum chemical method. The two calculated energy values both exhibit a linear correlation with the existing 29Si NMR chemical shift and the IR hydroxyl stretching frequency data. The inter-convertibility between different Si(nAl) sites during an alumination or dealumination process is also evaluated based on the calculated substitution energy. The results indicate that alumination processes are less favorable to occur in zeolites than dealumination processes and the latter is more likely to occur for Si(nAl) clusters that contain the maximum number of aluminum nearest neighbors. 相似文献
92.
紫外光引发LDPE膜接枝含氟丙烯酸酯的研究 总被引:7,自引:0,他引:7
通过紫外光引发表面接枝聚合反应的方法 ,把含氟丙烯酸酯单体R 5 6 1 0引到LDPE薄膜上 .对经丁酮抽提后的接枝膜进行FTIR、ESCA、SEM和DSC等表征 ,证实含氟聚合物以化学键的方式接枝在LDPE基体膜上 .在一定范围内 ,增加紫外光强、引发剂和单体浓度以及反应温度等均有利于提高接枝率 .经计算R 5 6 1 0的紫外光引发接枝聚合反应总活化能为 5 4 2kJ mol.接枝膜的接触角随着接枝率的提高逐步增大 ,直至趋于恒定 .作者提出接枝膜存在一个在接触角测定时影响基体膜与探测水滴相互作用过程的边界层 .当接枝率较低、接枝层厚度小于边界层临界厚度时 ,基体LDPE影响接触角的大小 ,但随着接枝率提高 ,接枝层逐渐变厚 ,氟聚合物层对接触角的贡献逐渐占优势 ,导致接触角随之增大 .当接枝率超过一定值以后 ,接枝层厚度超过边界层临界厚度 ,接枝层对接枝膜的接触角起全部贡献 ,接触角测定值随之稳定 相似文献
93.
Sonia M AlessoZhanru Yu David PearsPaul A Worthington Richard W.A LukeMark Bradley 《Tetrahedron》2003,59(36):7163-7169
The preparation, characterisation and application of a series of non-grafted polystyrene (PS) resins containing a styrenic methoxypoly(ethylene glycol) (MPEG) derivative is presented. These novel PS-MPEG resins were designed to balance swelling and solvation with improved handling. The monomer, 1-[2-(2-methoxyethoxy)ethoxy]-4-vinyl-benzene, contained an inert phenyl ether linkage designed to provide broad chemical compatibility and stability, yet imparting all the favourable properties of the PEG group into the new resin, whilst maintaining a high loading capacity. The synthetic performance of the new resins compared very favourably to those of TentaGel™, ArgoGel™ and aminomethyl PS. 相似文献
94.
Kelly M ElkinsDonald J Nelson 《Coordination chemistry reviews》2002,228(2):205-225
Aluminum ion (Al3+) in the ‘free’ (aquo) state is becoming increasingly prevalent in environmental waters, especially fresh waters, as a consequence of acid rain and other environmental processes. As Al3+ ion is known to affect markedly a wide range of biological systems, and since the presence of Al3+ in humans has been linked to a number of human diseases, it is important to understand the speciation of Al3+ ion in natural waters. Since some of the most important complexation agents for Al3+ in both fresh and sea waters are members of the complex humic substances group, it is important to understand the manner in which Al3+ interacts with this class of molecules, especially since binding of Al3+ to these molecules can effectively increase the bioavailability of this toxic metal ion to biological systems. The objective of this review is to present the current state of our understanding of aqueous aluminum complexation with the most acidic members (and therefore the most likely candidates for serving as Al3+ complexing agents) of the humic substances group, the fulvic acids. Much of the current knowledge has been revealed by comprehensive fluorescence titration analyses. Some additional information has come from other experimental approaches, including infrared spectroscopy, nuclear magnetic resonance spectroscopy, and a variety of electrochemical approaches. In this review, we also report on the results of our recent fluorescence and IR spectroscopy survey of the interaction of metals from of all three Nieboer and Richardson categories of environmental metals (Class A, Class B and Intermediate Class) with the fulvic acid sub-group of the humic substances. This has proven helpful in understanding some of the unique spectral behaviors of the Al3+-fulvic acid complex vis-a-vis fulvic acid complexes with many other metal ions. The results of our fluorescence and IR experiments with the model compounds, such as salicylic and phthalic acids, have allowed confirmation of the important roles played by both salicylic acid-like sites and phthalic acid-like sites in the unique complexation of Al3+ to humic substances, and help to explain some of the observed spectroscopic changes associated with Al3+ ion complexation to humic material. From the current work, it seems clear that major sources of the deviation in spectral properties between Al3+ and many other metal ions (across all three Nieboer and Richardson categories) are the unusually high value of its charge density and relatively low propensity for involvement in covalent bonding interactions (i.e. a very high ionic index combined with a relatively low covalent index in the Nieboer and Richardson classification of environmental metals), as well as affinity for certain functional groups. 相似文献
95.
Summary High pressure liquid chromatographic methods for the determination of diphenylmethane-4,4-diisocyanate (MDI) and toluene diisocyanate (TDI) in chemical products are described. The MDI- and TDI monomers were determined as their urea derivative formed by the reaction with 9-(methyl aminomethyl)-anthracene. Using these methods MDI- and TDI monomer concentrations have been determined in 55 chemical products: sealing waxes, insulating- and adhesive foam, hardener, primer, adhesives and surface coatings. The recovery of both MDI and TDI monomers from various types of chemical product was found to be 92–97%, and the relative standard deviations of the methods was <5% for all types of products. 相似文献
96.
4,4′-二(硬脂酰胺基)二苯甲烷(BSDM)能在乙烯基类单体中进行聚集、自组装,并可使苯乙烯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸-2-羟基乙酯等凝胶化,形成相应的分子凝胶.凝胶/溶胶相变温度(TGS)与BSDM浓度有关,BSDM质量分数越大,凝胶体系中分子间氢键和π-π键越多,要破坏它们所需要的能量越高,TGS因而也就越高.透射电镜表明,BSDM在各种可聚合溶剂中通过分子间相互作用形成类似纤维状的聚集体结构.BSDM在可聚合溶剂聚合前后的偏光显微照片表明,BSDM在体系中的晶型结构是球晶. 相似文献
97.
A reliable method for direct synthesis of β‐dichlorosubstituted acetanilides is reported. The key transformation involves the oxidative and catalytic cleavage of a carbon‐carbon bond in the presence of iodine trichloride (ICl3). In this protocol ICl3 is used not only as the catalyst but also as the oxidant which widely broadens the scope of its application in organic synthetic chemistry. 相似文献
98.
Frantisek Mikes Hongxiang Teng Yasuhiro Koike Yoshiyuki Okamoto 《Journal of polymer science. Part A, Polymer chemistry》2012,50(22):4717-4720
Copolymerizations of hexafluoroisobutylene (HFIB) with vinyl pentafluorobenzoate (VPFB) and vinyl trifluoroacetate (VTFA) were carried out in bulk using perfluorodibenzoyl peroxide as the radical initiator. The copolymers obtained were characterized by proton and fluorine NMR spectroscopy. The monomer reactivity ratios in the polymerization of HFIB with VPFB were r1 (HFIB) = 0, r2 (VPFB) = 0.373, and r1r2 = 0. The results indicated that these copolymers have alternating structures. Similarly, the copolymers of HFIB and VTFA also showed alternating structures. The films of HFIB‐co‐VPFB were prepared by casting THF solution of polymers. Films obtained were flexible and transparent. The refractive indices of copolymers were 1.4549, 1.4490, and 1.4438 at 532, 633, and 839 nm, respectively. The average Tgs of HFIB‐co‐VTFA and HFIB‐co‐VPFB were 52 and 71 °C, respectively. From these results, the Tg of the hypothetical HFIB homopolymer is postulated to be in between 70 and 90 °C, which may be useful in the assessment of Tgs of HFIB copolymers with other vinyl monomers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
99.
Jie Miao Weiwei He Lifen Zhang Yi Wang Zhenping Cheng Xiulin Zhu 《Journal of polymer science. Part A, Polymer chemistry》2012,50(11):2194-2200
In this work, living radical polymerizations of a water‐soluble monomer poly(ethylene glycol) monomethyl ether methacylate (PEGMA) in bulk with low‐toxic iron catalyst system, including iron chloride hexahydrate and triphenylphosphine, were carried out successfully. Effect of reaction temperature and catalyst concentration on the polymerization of PEGMA was investigated. The polymerization kinetics showed the features of “living”/controlled radical polymerization. For example, Mn,GPC values of the resultant polymers increased linearly with monomer conversion. A faster polymerization of PEGMA could be obtained in the presence of a reducing agent Fe(0) wire or ascorbic acid. In the case of Fe(0) wire as the reducing agent, a monomer conversion of 80% was obtained in 80 min of reaction time at 90 °C, yielding a water‐soluble poly(PEGMA) with Mn = 65,500 g mol?1 and Mw/Mn = 1.39. The features of “living”/controlled radical polymerization of PEGMA were verified by analysis of chain‐end and chain‐extension experiments. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
100.
Niels ten Brummelhuis Marcus Weck 《Journal of polymer science. Part A, Polymer chemistry》2014,52(11):1555-1559
Reversible addition‐fragmentation chain‐transfer (RAFT) polymerization was used to control the alternating copolymerization of styrene and 2,3,4,5,6‐pentaflurostyrene. The RAFT polymerization yields a high degree of control over the molecular weight of the polymers and does not significantly influence the reactivity ratios of the monomers. The controlled free‐radical polymerization could be initiated using AIBN at elevated temperatures or using a redox couple (benzoyl peroxide/N,N‐dimethylaniline) at room temperature, while maintaining control over molecular weight and dispersity. The influence of temperature and solvent on the molecular weight distribution and reactivity ratios were investigated. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1555–1559 相似文献