共查询到20条相似文献,搜索用时 46 毫秒
1.
2.
3.
4.
5.
离分子混合物溶液在极稀浓度区的粘度异常行为 总被引:1,自引:0,他引:1
上世纪50年代初人们就发现,高分子溶液的粘度在极稀浓度区往往表现出异常行为,即当浓度低于某一特定值后,比浓增比粘度浓度图偏离预计的线性关系,出现上弯或下弯的曲线.几十年来人们对此现象展开了大量研究,提出了一些互不协同的解释[1,2].最近,程时等[3,4]对该问题作了系统深入的研究,指出这种粘度异常是源于粘度测量中高分子溶液与毛细管内壁间的界面作用,并给出了消除界面作用干扰的理论改正公式.至此,单一高分子溶液粘度的异常问题得到了明确的解释.但是,关于高分子混合物在极稀浓度区的粘度行为的研究就比较稀少.80年代Dondos… 相似文献
6.
测定了不同分子量聚氧化乙烯(PEO)在水和苯溶剂中的粘度,发现在低浓度区PEO水溶液的比浓粘度出现负偏离, PEO苯溶液比浓粘度与浓度之间依旧满足线性关系.表面张力测定结果表明, PEO分子显著降低了水的表面张力,而苯的表面张力则不受影响.PEO水溶液和纯溶剂水表面张力的不同干扰了高分子溶液和溶剂在粘度计中流过时间的测量,导致低浓度区PEO水溶液比浓粘度出现负偏离.利用PEO水溶液和水表面张力测定结果,结合乌式粘度计的几何尺寸,定量分析了PEO水溶液和纯溶剂水表面张力的差异对粘度测量结果的影响,计算结果与实验结果基本相符.如果用PEO水溶液流过时间对浓度作图的外推值t0*计算相对粘度,可以完全消除PEO水溶液和水表面张力差异对粘度测量的影响. 相似文献
7.
8.
高分子在固体表面上的吸附层厚度对了解其结构具有重要意义.厚度的测量通常采用椭圆偏振法、流体力学法和沉降法等几种方法来测量[1].流体力学法始创于50年代中期Ohrn[2]对极稀高分子溶液粘度异常行为的解释.由于高分子在粘度计的毛细管管壁上的吸附,致使... 相似文献
9.
10.
本文从高分子溶液粘度和浓度依赖性中的斜率系数和高分子溶液流动时的流体力学及热力学因素之间关系着手,由9种高分子-溶剂体系的粘度数据,建立了一个新的一点法测定特性粘数方程。即: [η]=η_(sp)/c/(1+1/2(1-x)η_(sp)) 此式不仅是一个一点法测定特性粘数的新的方程,而且也是一个由高分子溶液粘度数据估计高分子-溶剂相互作用参数X的方程。 相似文献
11.
An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions. 相似文献
12.
An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction. 相似文献
13.
The Diels-Alder reactivity of 1,2-heteroborines (H4C4B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed. 相似文献
14.
Xi-Liu YunWen-Ying Bi Jian-Hui HuangYu Liu Daisy Zhang-NegrerieYun-Fei Du Kang Zhao 《Tetrahedron letters》2012,53(38):5076-5080
A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd2(dba)3-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring. 相似文献
15.
Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles. 相似文献
16.
An efficient and benign method for the preparation of aminomethyl-substituted fullerenes has been developed. The process, involving catalyst free, visible-light irradiation of 10% EtOH-toluene solutions containing fullerene C60 and N-trimethylsilylmethyl-substituted amines by using a 20 W compact fluorescent lamp, leads to formation of aminomethyl-substituted fullerene adducts in a highly efficient manner. The photoaddition reaction takes place via a pathway initiated by visible light absorption by C60, followed by SET from the amine to the triplet excited state of C60. Ethanol-promoted desilylation of the resulting a minimum radical then generates the corresponding α-amino radical which couples with the C60 radical anion to form the anion precursor of the fullerene adducts. The new approach using visible-light takes place under mild conditions and it does not require the use of photocatalysts. Thus, the method developed in this effort could broadens the range of functionalized fullerene derivatives that can be readily prepared. 相似文献
17.
Viktor A. Dmitriev Mariia M. Efremova Alexander S. Novikov Vladimir V. Zarubaev Alexander V. Slita Anastasia V. Galochkina Galina L. Starova Andrey V. Ivanov Alexander P. Molchanov 《Tetrahedron letters》2018,59(24):2327-2331
The reactions of various nitrones with indolyl- and pyrrolylacrylates proceeds regioselectively with high diastereoselectivity in the case of aldonitrones, and represents an effective method for obtaining new indolyl- and pyrrolyl-substituted isoxazolidine carboxylates stabilized by weak (CH?O) and moderate (NH?N) strength intramolecular hydrogen bonding. The resulting cycloadducts exhibit promising in vitro anti-influenza activities. 相似文献
18.
A transition metal-free method for the direct amination of benzoxazoles using formamides as nitrogen sources is reported, which was mediated by an inexpensive and environmentally friendly tetrabutylammonium iodide/tert-butyl hydroperoxide system and gave the 2-aminobenzoxazole derivatives with moderate to good yields. 相似文献
19.
Multifunctionalized 1,2,3,4-tetrahydropyridines are concisely synthesized in good yields via l-proline-catalyzed or l-proline/FeCl3-cocatalyzed one-pot multicomponent reactions (MCRs). The MCRs involve a domino hydroamination/prins reaction/Mannich-type reaction/intramolecular dehydration-cyclization process. The molecular structure of 5baa, one of multifunctionalized 1,2,3,4-tetrahydropyridines, was confirmed by single-crystal X-ray diffraction. 相似文献
20.
Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction
Laurent Gavara Thomas Boisse Jean-Pierre Hénichart Adam Daïch Philippe Gautret 《Tetrahedron》2010,66(38):7544-5571
In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments. 相似文献