Preparation and Properties of Epoxy Resins Containing Quinazolone Rings

Epoxy resins containing quinazolone rings were synthesized and characterized. Epoxy resins were made by reacting bisquinazolone phenol or bisquinazoline with epichlorohydrin or the diglycidyl ether of Bisphenol A. These resins were analyzed by DSC, GPC, IR, and NMR. The electrical and mechanical properties of the cured resins were evaluated. They have glass transition temperature above 200°C and excellent thermal stability, and T_g increases in the order of o-, m-, p-substituted phenol groups.     

多胺配体及其配合物的合成与热力学性质研究

合成并表征了5个多胺配体N，N′-二(1，10-菲罗啉-2-亚甲基)-1，2-乙二胺(L1)，1，7-二(1，10-菲罗啉-2-亚甲基)-1，4，7-三氮杂庚烷(L2)，1，10-二(1，10-菲罗啉-2-亚甲基)-1，4，7，10-四氮杂癸烷(L3)，1，13-二(1，10-菲罗啉-2-亚甲基)-1，4，7，10，13-五氮杂十三烷(L4)，N，N′-二(1,10-菲罗啉-2-亚甲基)-1，3-丙二胺(L5)。利用pH电位滴定法在25.0 ± 0.1 ℃时测定了这5个配体的质子化常数及其与Co(Ⅱ)，Ni(Ⅱ)，Cu(Ⅱ)和Zn(Ⅱ)形成配合物的稳定常数，并且试图解释了这5个系列配合物的差异。     

侧基含可光交联肉桂酸酯基的光敏聚苯乙烯的合成及其性能

采用氯甲基化试剂氯甲醚对聚苯乙烯(PS)实施了氯甲基化反应,然后使肉桂酸与氯甲基化聚苯乙烯(CMPS)的苄氯基团在碱性条件下发生亲核取代反应,成功制得了可光交联的光敏聚苯乙烯。利用1H-NMR、FT-IR、UV-Vis、TGA等测试手段对该聚合物的结构和热性能进行了表征及测试。探讨了反应时间对氯甲基化反应和接枝反应的影响。结果表明,合成得到的光敏PS具有良好的溶解性、热性能以及光敏性。     

磺酰胺型多齿配体的合成

有机金属配合物涉及了许多重要的生命过程,配体和配合物的合成及性质研究都越来越受到人们的重视。磺酰胺类化合物,磺酰胺中氨基氢的酸性可与酚类化合物相比拟,对金属离子有较强的配位能力,并且比酚试剂不易氧化,还可改变磺酰胺的空间体积和亲脂性。本文报道一类新的磺酰胺型多齿配体的合成,并证明它们能与金属离子形成配合物。     

交联聚苯乙烯氨基树脂的结构与脱色性能研究

通过改变交联度、致孔剂以及胺化试剂合成了一系列大孔氨基吸附树脂。详细研究了树脂孔结构、功能基结构与树脂脱色性能的关系。     

Multidentate Acyclic Neutral Ligands and Their Complexation

The properties of cyclic crown ethers are approximated by acyclic neutral ligands (popdands), which are compared and contrasted with open-chain bioionophores and acidic chelating agents in this article. Variations of the endo-polarophilicity/exo-lipophilicity balance, complex stability, ion slectivity can often be accomplished more easily, with greater versatility, and at less expense with acyclic polyethers than with their cyclic counterparts; complexation and decomplexation are generally faster in acyclic systems; and the pseudocavity usually has greater conformational flexibility. Acyclic crown ethers and open-chain cryptands stiffened by rigid “terminal groups” containing donor atoms readily form crystalline complexes of alkali and alkaline earth metals. Some oppen-chain neutral ligands form helical conformations in their crycstalin complexes. The observed coordination numbers and geometries are of theoretical interst. Attractive terminal group interactions lead to pseudocyclic species occupying a position intermediate between cyclic and acyclic ligands. It has recently proved possible to isolate crystalline complexes of alkali and alkaline earth metal ions with weakly donating oligo(ethylene glycol ethers) and with glycols; such complexes have also been obtained with sugars. Acyclic neutral ligands can serve as simple models of nigericin-type bioionophores and be used analytically in microelectrodes. The recently discoverd crystalline stoichiometric complexes formed by some acyclic neutral ligands with guest molecules such as urea, thiourea, and water provide a fresh insight into weak interactions between neutral molecules and for the development of urea receptors.     

Synthesis,Characterization, and Fluorescence Chemosensor Properties of a cis‐Dioxomolybdenum(VI) Complex Containing Multidentate Hydrazone Ligands

The homobimetallic molybdenum(VI) complex, [(MoO₂)₂(slsch)(DMF)₂], derived from multidentate hydrazone ligand (H₄slsch = disalicylaldehyde succinoyldihydrazone) was synthesized. The complex was obtained by reaction of the ligand with Mo₂(acac)₂ in 1:2 molar ratio in methanol. It was characterized by using various spectroscopic techniques. The structure of the complex was established by single crystal X‐ray diffraction. The complex shows fluorescence emission, responds toward Al^III ions, and hence it can be used as fluorescence chemosensor for sensing Al^III ions. The sensing properties show that the complex is more efficient and sensitive towards Al^III ions than the rest of the ions used in the presented study.     

The Coordination Chemistry of Multidentate Isocyanide Ligands

In spite of the excellent ligation properties of isocyanides, until a few years ago there was only a small number of known multidentate ligands of this type. One of the reasons for this lack of interest, when compared to monodentate isocyanides, was the linear arrangement of the M? C?N? R group, which usually inhibits the formation of mononuclear chelate complexes and leads to the formation of multinuclear or polymeric metal complexes. In these, the multidentate ligand acts in a monodentate fashion towards each metal atom. Only recently has a series of polyisocyanides with large ligand backbones been synthesized successfully. Bidentate isocyanides can bridge two metal atoms or react to give chelates with only one metal center. Tripodal ligands form mono- or binuclear complexes, in which the largest organometallic rings observed to date occur (up to 36 atoms). This class of ligands promises to be interesting for the synthesis of stable, diagnostically important technetium complexes of the type [Tc(CNR) ₆ ]⁺. There also appear to be applications for tripodal isocyanides in catalysis. A facial, chiral Cr(CNR^*)₃ unit might be able to catalyze the hydrogenation or isomerization of prochiral double bonds. It is even possible to bind triisocyanides with suitable backbones to carbonyl trimetal clusters, thereby stabilizing them, or making selective cluster formation possible. Coordinated isocyanides can be transformed readily into carbene ligands, which, in the future, could lead to complexes with polycarbene ligation.     

含混合多齿螯合配体双缺口立方烷型四核Mn配合物的合成、晶体结构与磁性研究

本文报道了一个含混合多齿螯合配体的四核Mn配合物Na₂[Mn₂^ⅢMn₂^Ⅱ(pdmH)₂(L)₂(N₃)₂]·2CH₃OH·2H₂O(1·2CH₃OH·2H₂O,pdmH₂为2,6-吡啶二甲醇,H₂L为2,6-吡啶二甲醇与2,2-二吡啶酮水合物的脱水物),并对其进行单晶结构分析、红外、元素分析和磁性研究。单晶结构分析表明,该化合物属于三斜晶系P1空间群,分子中2个Mn²⁺、2个Mn³⁺及6个来自pdmH-或L^2-配体的O原子构成1个双缺口立方烷结构。磁性研究表明Mn²⁺与Mn³⁺之间为弱的反铁磁性耦合作用(J₁=-0.89cm^-1,J₂=-1.13cm^-1),Mn³⁺离子之间为稍强的铁磁性耦合作用(J₃=3.20cm^-1),基态自旋值S=2,交流磁化率研究表明,在所测试条件下,其虚部没有表现出单分子磁体所具有的频率依赖现象。     

含混合多齿螯合配体双缺口立方烷型四核Mn配合物的合成、晶体结构与磁性研究

本文报道了一个含混合多齿螯合配体的四核Mn配合物Na2[MnIII2MnII2(pdmH)2(L)2(N3)2]·2CH3OH·2H2O(1·2CH3OH·2H2O,pdmH2为2,6-吡啶二甲醇,H2L为2,6-吡啶二甲醇与2,2-二吡啶酮水合物的脱水物),并对其进行单晶结构分析、红外、元素分析和磁性研究。单晶结构分析表明,该化合物属于三斜晶系P1空间群,分子中2个Mn2+、2个Mn3+及6个来自pdmH-或L2-配体的O原子构成1个双缺口立方烷结构。磁性研究表明Mn2+与Mn3+之间为弱的反铁磁性耦合作用(J1=-0.89 cm-1,J2=-1.13 cm-1),Mn3+离子之间为稍强的铁磁性耦合作用(J3=3.20 cm-1),基态自旋值S=2,交流磁化率研究表明,在所测试条件下,其虚部没有表现出单分子磁体所具有的频率依赖现象。     

The Synthesis of Novel Sulfur-containing Chiral Macrocyclic Multidentate Ligands

The biomimetic chemistry has aroused widespread interest in the past two decades^[l~4]. The molecular recognition property of chiral crown ether has attracted much attention, not only due to its wide applications to pharmaceutical science, catalysis, and separation technology but also because the inclusion process is considered an ideal model mimiching the enzyme-substrate interaction.     

基于多齿希夫碱配体的四核和十核锰簇合物的合成、结构和磁性

合成了一种具有{NO₄}给电子组成的多齿水杨醛希夫碱配体,3,5-二-叔丁基水杨醛-三(羟甲基)氨基甲烷(H₄L),并利用元素分析、红外光谱以及核磁共振氢谱表征其结构。Mn(ClO₄)₂或MnCl₂·4H₂O分别与该配体在溶液中反应生成了一个四核锰簇合物[Mn^III₄(HL)₂(H₂L)₂(MeCN)₄](ClO₄)₂·2MeCN(1)和一个十核锰簇合物[Mn^III₆Mn^II₄(bz)10(L)₄(H₂O)₂]·10MeCN(2)。X-射线衍射分析表明化合物1的晶体结构空间群为三斜P1,而化合物2为正交Aba2。2~300 K温度区间的磁性测量数据表明化合物2中存在反铁磁相互作用。     

基于多齿希夫碱配体的四核和十核锰簇合物的合成、结构和磁性

合成了一种具有{NO₄}给电子组成的多齿水杨醛希夫碱配体,3,5-二-叔丁基水杨醛-三(羟甲基)氨基甲烷(H₄L),并利用元素分析、红外光谱以及核磁共振氢谱表征其结构。Mn(ClO₄)₂或MnCl₂·4H₂O分别与该配体在溶液中反应生成了一个四核锰簇合物[Mn₄^Ⅲ(HL)₂(H₂L)₂(MeCN)₄](ClO₄)₂·2MeCN(1)和一个十核锰簇合物[Mn₆^ⅢMn₄^Ⅱ(bz)₁₀(L)₄(H₂O)₂]·10MeCN(2)。X-射线衍射分析表明化合物1的晶体结构空间群为三斜P1,而化合物2为正交Aba2。2~300K温度区间的磁性测量数据表明化合物2中存在反铁磁相互作用。     

新型侧基含磷共聚酯的合成、表征及性能

以精制对苯二甲酸（TPA）、乙二醇（EG）和含磷反应型阻燃剂9,10-二氢-9-氧杂-10-[2,3-二（2-羟基乙氧基）羰基丙基]-10-磷杂菲-10-氧化物为原料,利用熔融缩聚法合成了含磷量分别为0．35％、0．65％的阻燃聚酯。通过熔融纺丝法将聚酯制成纤维及织物,研究了纤维的染色性能,并通过极限氧指数法和垂直燃烧法研究了织物的阻燃性能。FT-IR和NMR研究结果表明：阻燃共聚酯含磷量为0．35％时,其氧指数（LOI）达31．5％,并无熔滴、烟雾产生,具有优异的阻燃性能和抗熔滴性能。DSC、TG和XPS的研究结果表明：侧基舍磷单元的引入降低了聚酯的Tg和Tm,较低的Tm将有利于材料加工性能的改善;阻燃聚酯侧基上的P-C、P-O键易断裂并挥发至气相中,从而降低了聚酯热稳定性,阻燃聚酯可能以气相阻燃机理为主发挥阻燃作用。此外,含磷共聚酯纤维具有较优异的染色性能。     

Friedel-Crafts酰基化法制备聚苯乙烯型阴离子交换树脂

提出了一种合成聚苯乙烯型阴离子交换树脂的新方法：通过Ｆｒｉｅｄｅｌ－Ｃｒａｆｔｓ酰基化反应在交联聚苯乙烯上引入乙酰基，然后经溴化、胺化反应制备阴离子交换树脂。该方法避免了使用氯甲醚等致癌物质，并消除了二次交联等副反应。讨论了溶剂，催化剂，试剂和反应温度及时间等因素对各步反应的影响。测定了产物的基本性能并对所得结果进行了讨论。     

九种Salen型多齿新配体的合成

利用乙二胺及其衍生物的Mannich反应在无催化剂的条件下合成了9种Salen型新的配体,化合物1和2在无溶剂条件下合成,化合物3a～3g在Salen配体中引入呋喃杂环,对其与金属的配位提供了多种可能性.所得化合物结构经元素分析,IR,MS,1H NMR等确认,同时用X射线单晶衍射测定了化合物1和3b的晶体结构.     

螯合树脂研究（XXVI）氮杂冠醚型树脂的合成及其吸附性能

用环氧氯丙烷低聚物分别与二（三）乙醇胺的钠盐进行反应，合成了两种氮杂冠醚型交联树脂．研究了树脂对贵金属和一些个过渡金属的吸附性能．树脂对Ａｕ（Ⅲ）具有较高的吸附容量和吸附率。在Ｃｕ（Ⅲ）－Ｐｄ（Ⅱ）－Ｐｔ（Ⅳ）混合液中优先吸附Ａｕ（Ⅲ）；在Ｃｕ（Ⅱ）—Ｚｎ（Ⅱ）和Ｃｕ（Ⅱ）—Ｃｏ（Ⅱ）—Ｎｉ（Ⅱ）的混合液中只吸附Ｃｕ（Ⅱ）而不吸附其他金属离子．