芴-氮杂萘酮-聚芳醚酮离聚物的合成与性能

以双酚芴、双酚A型二氮杂萘酮、二氟二苯酮和二氟二苯酮磺酸钠为原料, 通过调整4种单体的比例以及加料顺序控制缩聚反应, 制备了一系列具有不同离子交换容量的含芴和二氮杂萘酮联苯单元的嵌段聚芳醚酮, 简称芴-氮杂萘酮-聚芳醚酮离聚物. 采用黏度测试、傅里叶衰减全反射红外光谱(FTIR-ATR)、氢谱(1H NMR)和热失重(TGA)等分析方法, 对不同结构的芴-氮杂萘酮-聚芳醚酮离聚物的分子量、结构及热稳定性进行了表征. 实验结果表明, 采用控制缩聚法能够制备出不同离子交换容量的高分子量芴-氮杂萘酮-聚芳醚酮离聚物, 该系列离聚物具有良好的热稳定性. 对该系列离聚物膜进行了抗氧化性、水解稳定性、吸水率、耐醇性、离子交换容量和质子传导率测试. 测试结果表明, 该系列离聚物具有良好的抗氧化性、水解稳定性、耐醇性、质子传导率和适当的吸水率.     

邻羟基苯基重氮氨基偶氮苯与季铵盐型表面活性剂显色反应的研究及应用

研究了显色剂邻羟基苯基重氮氦基偶氛苯(HDAA)与季铵盐型表面活性剂的显色反应。在0．1mol·L-1的氢氧化钠介质中,试剂与溴化十六烷基三甲胺(CTMAB)、溴化十六烷基吡啶(CPB)和氯化十六烷基吡啶分别形成玫瑰红色离子缔合物,缔合比均为13,CTMAB体系λmax＝558nm,CPB和CPC体系λmax＝562nm,表观摩尔吸光系数分别为1．34×104,1．03×104和1．47×104L·mol-1·cm-1。探讨了微量CTMAB、CPB和CPC的测定方法,结果满意。     

含二苯并-18-冠-6冠醚环的主链型液晶共聚酯的设计与合成(英文)

以4,4′-(α,ω-亚烷基二酰氧)二联苯甲酰氯(M1)、顺式-4,4′-双(4-羟基苯基偶氮)二苯并-18-冠-6(M2)、反式-4,4′-双(4-羟基苯基偶氮)二苯并-18-冠-6(M3)和1,10-癸二醇(M4)为单体,通过溶液共缩聚反应,合成了两个系列新的含联苯型液晶基元和偶氮型冠醚环的主链型液晶共聚酯.共聚酯的[η]在0·25～0·35和0·27～0·38之间.单体的化学结构通过IR、UV-Vis、1H-NMR、MS和元素分析等方法确证.共聚酯的性质采用[η]、DSC、TGA、WAXD和POM等方法进行了研究.发现所有的共聚酯加热到各自熔融温度以上都能形成向列相液晶态,可以观察到向列相的丝状织构或纹影织构或球粒织构.共聚酯的熔融温度(Tm)和各向同性温度(Ti)随共聚酯分子中柔性间隔基长度的增加而有规律地降低,含反式冠醚环的共聚酯的Tm和Ti均高于相应含顺式冠醚环的共聚酯的Tm和Ti.     

芴基Cardo型聚亚胺酮的分子结构拟、合成及性能

以9,9-双-(3-R-4-氨基苯基)芴(R=H,CH3,F)和1,4-双-(4′-溴苯酰基)苯为单体,通过BuchwaldHartwig交叉偶联反应,缩聚合成了芴基Cardo型聚亚胺酮(PIKF).利用MS软件对其分子结构进行模拟,并通过1H NMR和FTIR等方法进行表征,结果与目标产物吻合.利用凝胶渗透色谱(GP...     

新型若丹宁试剂光度法测定镍的研究

利用合成的新型试剂3 对氟苯基 5 (2′ 羧基苯偶氮)若丹宁与金属镍进行显色反应,发现在表面活性剂存在下,新型若丹宁显色剂与镍有较灵敏的反应,镍量在0～25μg/10ml范围内符合比耳定律,其表观摩尔吸光系数为2.3×104L·mol-1·cm-1,可用于水及茶叶中镍的测定。     

用DCNPNPT测定江水中季铵盐型阳离子表面活性剂

利用三氮烯类试剂与季铵盐型阳离子表面活性剂形成离子缔合物可用于季铵盐型阳离子表面活性剂的测定。如用HDNPAPT[1]、HDAA[2]测定CTMAB、CPB,但其灵敏度有待提高。本文研究了显色剂1 (2,6 二氯 4 硝基苯) 3 (4 硝基苯) 三氮烯(DCNPNPT)[3]与阳离子表面活性剂的显色反应,结果表明,DCNPNPT与CTMAB、CPB反应的表观摩尔吸光系数分别为3 93×104L·mol 1·cm 1,和4 16×104L·mol 1·cm 1,是目前报道的用光度法测定季铵盐型阳离子表面活性剂较灵敏的体系之一。用此法测定了瓯江水中微量阳离子表面活性剂CTMAB、CPB的…     

3-对甲苯基-5-(2′-胂酸基苯偶氮)若丹宁光度法测定镍

合成了新型试剂3 对甲苯基 5 (2′ 胂酸基苯偶氮)若丹宁,研究了在表面活性剂存在下试剂与镍的显色反应,建立了光度法测定镍的新方法,其表观摩尔吸光系数为2.6×104L·mol-1·cm-1,镍量在0～20μg/10mL范围内符合比耳定律,可用于水及茶叶中镍的测定。     

含二氮杂芴基的旋光环氧化合物的合成及聚合研究

以1,10-邻菲罗啉(1)为原料制备4,5-二氮芴-9-酮(2),并合成4,5-二氮杂芴(3)和9-亚甲基-4,5-二氮杂芴(5),再利用正丁基锂(或甲基锂)与上述两种二氮杂芴反应得到相应的锂盐,在-50℃下与旋光的环氧氯丙烷(ee98%)反应得到光学纯的含二氮杂芴基取代末端环氧化合物,它们的ee值均大于98%.将4,5-二氮芴-9-酮与乙基溴化镁(或苯基溴化镁)反应,得到相应的叔醇.叔醇在氢氧化钾和四丁基溴化铵存在下,与旋光的环氧氯丙烷反应,也得到光学纯的含二氮杂芴基取代末端环氧化合物,ee值均大于97%.将末端环氧化合物在不同条件下聚合,得到分子量分布很窄的含二氮杂芴基的聚醚.通过核磁共振、元素分析、凝胶渗透色谱等手段对产物进行了表征,对影响聚合的相关因素做了探讨.     

新显色剂对胂酸基苯基重氮氨基偶氮苯的合成及其与Cd（Ⅱ）的显 …

合成了对胂酸基苯基重氮氨基偶氮苯并对其与Cd(Ⅱ)的显色反应进行了初步研究。在pH 10．5的碱性介质中,在Triton X-100存在下,试剂与Cd(Ⅱ)的显色反应有较高灵敏度,摩尔吸光系数ε472=9．1×104L·mo1-1·cm-1,在0～10μg／25 mL范围内遵守比耳定律。方法应用于分离后的井水和湖水中Cd(Ⅱ)的测定,结果满意。     

含异亚丙基聚亚胺醚酮的合成与性能

首先通过Friedel-Crafts酰基化反应得到1,4-双-(4′-溴苯酰基)苯,经两步合成芳香二胺2,2-双-[4-(4-氨基苯氧基)苯基]丙烷,以1,4-双-(4′-溴苯酰基)苯和2,2-双-[4-(4-氨基苯氧基)苯基]丙烷为单体,以三(二亚苄基丙酮)二钯为催化剂,1.1′-联萘-2.2′-二苯膦(BINAP)为配体,由钯催化的胺基化反应缩聚合成了高分子量含异亚丙基聚亚胺醚酮(pr-PIEK),Mn=5.15×104、Mw=1.26×105.其结构由红外、核磁氢谱和元素分析表征,表征结果与目标结构吻合良好.通过XRD、DSC和TG等对pr-PIEK的主要性能进行分析,结果表明pr-PIEK为无定形态,表现出良好的热稳定性(高的热分解温度TD>450℃)、力学性能(拉伸强度为72.76 MPa、拉伸模量为1013.63 MPa、断裂伸长率为10.32%)和较好的溶解性能,pr-PIEK在室温条件下可溶解在普通有机溶剂氯仿中,50℃溶于丙酮.     

Transferability of interatomic correlation energies

A simple procedure is presented to estimate the interatomic correlation energy of a bond A-B on the basis of intrabond correlations of the homopolar parents A-A and B-B and the bond polarity of A-B. We use a local approach supplemented by a semiempirical mean-field Hamiltonian within the bond orbital approximation. The capability of the interpolation scheme is demonstrated for several molecules formed by main-group atoms.     

Assessment of relative stabilities of positional isomers of polyhedral heteronuclear clusters via a simplified method of bond energy calculations based on tight-binding approach and adjacent matrix method: applications to binary icosahedral clusters

A new and simple method for assessing the relative stabilities of various positional isomers of a given heteronuclear cluster is described. The method is based on a tight-binding approach in conjunction with an adjacent matrix methodology (TBAM). The usefulness of the method is illustrated by bond energy calculations of a number of binary icosahedral clusters, including noncentered icosahedral A(n)B(12)(-)n clusters comprising main-group elements B, C, N, and S as well as B- and A-centered icosahedral A(n)B(13)(-)n clusters that consist of transition metals, Au, Ag, Ni, and Pt atoms. The latter results are compared with the previously reported molecular mechanics calculations based on Lennard-Jones potential and with experimental results, whenever possible. The trends of the total bond energies obtained by the two methods are nearly parallel in all cases, indicating that the relative stabilities predicted by the two methods follow the same order. The TBAM approach provides a simple and efficient way of predicting the relative stabilities of various positional isomers of a given cluster, particularly for clusters where the number of positional isomers is so large that it cannot be handled manually. The total bond energies exhibit a stepwise progression. Each step is characterized by a set of A-A, B-B, and A-B bonds which uniquely determines the total bond energy and, hence, the stability. The step formation implies that positional isomers of a given cluster geometry can be categorized by sets of numbers of A-A, B-B, and A-B bonds, or simply the numbers of the minority (either A-A or B-B) bonds. Three site preference rules, the strong-bond rule, the heterobond rule, and the big-hole rule, were formulated based on these model calculations. These rules are useful in rationalizing and/or predicting the relative stabilities of various positional isomers of a given cluster geometry.     

Molecular simulation study of the effect of pressure on the vapor-liquid interface of the square-well fluid

We examine a model system to study the effect of pressure on the surface tension of a vapor-liquid interface. The system is a two-component mixture of spheres interacting with the square-well (A-A) and hard-sphere (B-B) potentials and with unlike (A-B) interactions ranging (for different cases) from hard sphere to strongly attractive square well. The bulk-phase and interfacial properties are measured by molecular dynamics simulation for coexisting vapor-liquid phases for various mixture compositions, pressures, and temperatures. The variation of the surface tension with pressure compares well to values given by surface-excess formulas derived from thermodynamic considerations. We find that surface tension increases with pressure only for the case of an inert solute (hard-sphere A-B interactions) and that the presence of A-B attractions strongly promotes a decrease of surface tension with pressure. An examination of density and composition profiles is made to explain these effects in terms of surface-adsorption arguments.     

Lattice Monte Carlo investigations on copolymer systems, 3. Alternating and random copolymers

Alternating and random copolymers in dilute solution are investigated by means of Monte Carlo simulations on a cubic lattice. Each molecule consists of an equal number of A and B segments, either randomly distributed along the chain or forming an alternating sequence. The energy parameters chosen represent selective solvent conditions (the solvent is a good one for monomers of type A and a θ-solvent for B; between A and B repulsive interactions are operative). Comparison with di- and triblock copolymers of equal overall composition reveals that the behaviour of random or alternating copolymers (subject to the same selective solvent) is quite different. Their properties rather resemble those of homopolymers in a solvent of intermediate quality. The absolute chain dimensions (e.g. the mean square radius of gyration, 〈s²〉, and the mean square end-to-end distance, 〈h²〉) of random and alternating copolymers as well as their scaling exponents are significantly larger than those of block copolymers. The ratio between 〈h²〉 and 〈s²〉 as well as the shape of the polymer (expressed by the asphericity δ) are similar to those of athermal polymers indicating that there is no pronounced selectivity of the solvent. In contrast to block copolymers, these parameters exhibit no significant chain-length dependence. The number of the various types of polymer-polymer contacts (A-A, B-B and A-B) is almost independent of the type of contact at least for the solvent conditions investigated. This is in contrast to block copolymers where A-B contacts are widely suppressed and where the number of B-B contacts is approximately twice as high as that of A-A contacts.     

The influence of interactions between reagents on the excess in the rate of quenching reaction: molecular dynamics study

The influence of the interactions between reagents on the excess in the rate coefficient, Deltak, for the instantaneous reaction A+B-->C+B have been investigated by performing large scale molecular dynamics simulations for simple soft spheres. The simulation method has enabled us to determine the contributions to Deltak coming from A-B as well as B-B interactions. The simulations have shown that positive values of Deltak that appear both for the liquid and for the Brownian system [M. Litniewski, J. Chem. Phys. 123, 124506 (2005); 124, 114501 (2006)] result from B-B interactions. If B-B interactions were absent, Deltak was always negative. The influence of B-B interactions was about three times higher for the Brownian system than for the liquid. A qualitative explanation for the effect has been proposed basing on a simple model and analyzing the influence of B-B interactions on fluctuations in concentrations of reagents. The influence of A-B interactions was completely negligible except for the liquid at short times, for which the cancellation of A-B interaction noticeably decreased Deltak.     

The global phase behavior of the two-component systems with intracomponent association: Flory approach

Within the Flory approach we study the phase diagrams of two-component fluids, the molecules of each component A(f(A)), B(f(B)) bearing f(A) (f(B)) functional groups capable of forming thermoreversible A-A and B-B bonds. We develop a general procedure to classify these diagrams depending on the values of four governing parameters -- entropies and normalized energies of A-A and B-B bonds, and give full topological classification of phase diagrams with f(A,B)> or =3. We show that these phase diagrams can have immiscibility loops and up to four critical points.     

Direct dehydration polycondensation of lactic acid catalyzed by water‐stable Lewis acids

Poly(L ‐lactic acid) (PLLA) is generally produced by ring‐opening polymerization of (S,S)‐lactide, which is prepared from dehydration polycondensation of lactic acid and successive depolymerization. Results of this study show that scandium trifluoromethanesulfonate [Sc(OTf)₃] and scandium trifluoromethanesulfonimide [Sc(NTf₂)₃] are effective for one‐step dehydration polycondensation of L ‐lactic acid. Bulk polycondensation of L ‐lactic acid was carried out at 130–170 °C to give PLLA with M_n of 5.1 × 10⁴ to 7.3 × 10⁴ (yield 32–60%). The solution polycondensation was performed at 135 °C for 48 h to afford PLLA with M_n of 1.1 × 10⁴ with good yield (90%). In no case did ¹H NMR, specific optical rotation, or DSC measurement confirm racemizations. The catalyst was recovered easily by extraction with water and reused for polycondensation. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5247–5253, 2006     

Friedel-Crafts Polymers. 8. Friedel-Crafts Polycondensation of β-Resorcylic Acid or Resorcinol with p-Xylylene Dichloride,p,p′-Dichloromethyldiphenyl Ether,and p,p′-Dichloroacetyldiphenyl Ether

Friedel-Crafts polycondensation of β-resorcylic acid (BRA) with p-xylylene dichloride (PXDC) or 4,4′-dichloromethyldiphenyl ether (DDE) in dioxane could be effected without simultaneous decarboxylation of BRA. The similar polycondensation of BRA with PXDC, DDE, or 4,4′-dichloroacetyldiphenyl ether (DADE) in nitrobenzene or in the absence of solvent at 150°C was associated with decarboxylation of BRA. Polymers having structures isomeric with those of the polycondensation product of BRA formed with subsequent in situ decarboxylation were prepared by Friedel-Crafts polycondensation of resorcinol with the above dichlorides. All the polymer samples were characterized, and those with related structures were compared. The ion-exchange properties of the polymer sample prepared from BRA and DDE in dioxane were studied.     

Cp*TiCl2N[Si(CH3)3]2/MAO催化剂合成无规聚丙烯弹性体

合成了Cp TiCl2 N[Si(CH3) 3]2 甲基铝氧烷 (MAO)催化体系 ,以该体系进行丙烯聚合得到无规聚丙烯 ,具有高的分子量及良好的弹性 ,玻璃化温度为 - 8 8℃ .产物经DSC、1 3C NMR、DMA等方法表征 .结果表明 ,催化活性随着丙烯压力的增加 ,有明显的增大 .催化活性在 4 0℃下有最高的催化活性 ,而产物分子量随着温度的下降有明显增大 ,在 0℃～ 5 0℃范围内分子量MW =(2 0～ 6 0 )× 10 4 .