混合配体、希土三元配合物的研究 Ⅳ.3,5二硝基水扬酸(H2DNSA)、邻菲咯啉(phen)、希土(RE)三元固体配合物的合成及性质

本文报道了十种希土元素与3,5-二硝基水扬酸、邻菲咯啉三元配合物的制备方法。通过元素和化学分析测定了化合物的化学组成,并用红外光谱、紫外光谱、差热分析、磁化率、X射线粉天衍射等对所合成的化合物进行了结构和性质的研究。     

配位滴定法连续测定铜和锌的新指示剂

对2-（3,5-二氨-2-吡啶偶氮）-5-二甲基苯胺（3,5-diCl-PADMAB）作指示剂络合滴定铜和锌进行了研究。在pH5．0的乙酸-乙酸钠介质中,以3,5-diCl-PADAMAB作指示剂,EDTA为滴定剂连续测定铜和锌,滴定终点颜色变化敏锐,准确度高,铜和锌量各在0～20mg范围内与EDTA量成正比。方法用于合金中铜和锌的测定,分析结果的相对标准偏差为〈0．1％和〈0．4％。     

Rhenium(IV) and rhenium(V) complexes with 3,5-dimethylpyrazole

Mono-and dinuclear Re^IV and Re^V complexes with 3,5-dimethylpyrazole (Me₂pzH) were synthesized. The cis-[Re₂O₃Cl₄(3,5-Me₂pzH)₄] complex (cis-1) was prepared by the reaction of NH₄ReO₄ with K[HB(Me₂pz)₃] in concentrated HCl or by refluxing of [ReCl₃(MeCN)(PPh₃)₂] with Me₂pzH in air. The bromide complex trans-[Re₂O₃Br₄(3,5-Me₂pzH)₄] (trans-2) was synthesized by passing dry HBr through a solution of [Re₂O₃Br₂(μ-3,5-Me₂pz)₂(3,5-Me₂pzH)₂] (4) in chloroform. The pyrazolate-bridged complex [Re₂O₃Cl₂(μ-3,5-Me₂pz)₂(3,5-Me₂pzH)₂] (3) was prepared from (Et₄N)₂[ReOCl₅] or Cs₂[ReOCl₅] and Me₂pzH. The corresponding bromide and iodide complexes [Re₂O₃X₂(3,5-Me₂pz)₂(3,5-Me₂pzH)₂] · C₆H₆ (X = Br (4) or I (5)) were synthesized by the reactions of (NH₄)₂[ReBr₆] or K₂[ReI₆], respectively, with Me₂pzH. The [ReO(OMe)(3,5-Me₂pzH)₄]Br₂ · · 3,5-Me₂pzH · 4H₂O complex (6) was obtained as a by-product in the synthesis of complex 4. The reaction of [ReNCl₂(PPh₃)₂] with Me₂pzH was accompanied by hydrolytic denitration giving rise to the mixed-ligand complex [Re₂O₃Cl₂(μ-3,5-Me₂pz)₂(3,5-Me₂pzH)(PPh₃)] (7). The reaction of (NH₄)₂[ReBr₆] with a Me₂pzH melt gave the trans-[ReBr₄(3,5-Me₂pzH)₂] · · Me₂CO complex (8). The structures of complexes 2 and 4–8 were established by X-ray diffraction. All compounds were characterized by elemental analysis, electronic absorption spectroscopy, ¹H NMR and IR spectroscopy, mass spectrometry, and cyclic voltammetry. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 52–59, January, 2006.     

新醚酮聚酰亚胺

二苯醚分别与对位和间位 硝基苯甲酰氯以及间苯二甲酰氯反应合成了五种醚酮双硝基化合物，经还原生成五种相应的二胺，其中，４，４′ 双（３ 氨基苯甲酰基）二苯醚（ＢＡＤＰＥ）分别与均四苯甲酸二酐（ＰＭＤＡ）、３，３′，４，４′ 二苯甲酮四甲酸二酐（ＢＴＤＡ）和４，４′ 氧化二邻苯二甲酸二酐（ＯＤＰＡ）聚合亚胺化后可生成橙色透明薄膜，其韧性好，拉伸强度高，耐溶剂，并有一定的耐强碱性．它们的Ｔｇ分别为２７３５、２３９和２２４℃，它们的高温氧化稳定性均很好，它与ＢＴＤＡ聚合而成的聚酰胺酸对铝／铝及铜／铜等金属都有极好的胶粘性，亚胺化后胶接强度极高．     

四氢呋喃开环均聚以及四氢呋喃和环硫氯丙烷共聚新催化体系

研究发现无水稀土氯化物 ５０％发烟硫酸体系是四氢呋喃（ＴＨＦ）均聚和四氢呋喃与环硫氯丙烷（ＣＭＴ）共聚合的优良新催化体系．考察了ＴＨＦ均聚反应特征，在合适条件下，ＴＨＦ聚合以６５％转化率制得粘均分子量达１０，０００～１５，０００的白色聚四氢呋喃（ＰＴＨＦ）固体．端羟基分析法测得聚合物的分子链两端均为羟基．考察了影响ＴＨＦ ＣＭＴ共聚合反应诸因素，如聚合温度和时间、两单体的比例等，制得数均分子量为１，０００左右的淡黄色粘性固体共聚物．     

混合配体、希土三元配合物的研究 Ⅳ.3,5—二硝基水扬酸(H_2DNSA)、邻菲咯啉(phen)、希土(RE)三元固体配合物的合成及性质

本文报道了十种希土元素与3,5-二硝基水扬酸、邻菲咯啉三元配合物的制备方法。通过元素和化学分析测定了化合物的化学组成,并用红外光谱、紫外光谱、差热分析、磁化率、X射线粉天衍射等对所合成的化合物进行了结构和性质的研究。     

防弹纤维性能预测新理论及PBO苯并恶唑环热稳定性表征

介绍一种预测防弹纤维性能的新理论(U*)1/3参数预测法,由Phoenix和Portwal理论公式推导出的(U*)1/3参数可以作为实际应用的指标参考.对PBX聚苯唑系刚性环热稳定性进行了表征,PBO热降解温度为650℃;采用热拉伸处理可使PBO纤维取向提高、结构更加完善,拉伸模量可达20～300 GPa.     

活性开环歧化合法合成带羧酸酯基功能高分子

由石油化工C5馏分提取得到的粗产品双环戊二烯(DCPD,83.9%)经精馏制成高纯度双环戊二烯(98.9%),解聚后制成环戊二烯(CPD).以CPD、丙烯酸叔丁酯(tBA)为原料经Diels-Alder反应合成得到了一种带叔丁氧羰基的降冰片烯衍生物-2-叔丁氧羰基-5-降冰片烯(BOCN).以钌卡宾络合物RuCl2(PCy3)2(=CHPh)为引发剂进行所合成降冰片烯基单体BOCN的活性开环歧化聚合(ROMP)反应,合成得到一种具有受控分子量及窄分子量分布的带羧酸酯基的反应性高分子.     

AMIDOXIMATION AND CHARACTERIZATION OF NEW COMPLEXING HYDROGELS PREPARED FROM N-VINYL 2-PYRROLIDONE/ACRYLONITRILE SYSTEMS

Solutions, obtained from the mixture of different mole ratios of N-vinyl 2-pyrrolidone and acrylonitrile, were irradiated in a ⁶⁰Co-γ source to produce copolymers. The swelling percentage curves were formed, and a diffusion exponent was calculated. For the uranyl ion adsorption, these copolymers were reacted with hydroxylamine hydrochloride to convert C≡N groups to ─C?N-OH (amidoxime) groups. The optimum amidoximation time was determined by uranyl ion adsorption. The structure of copolymers, before and after amidoximation, was analyzed with spectroscopic and thermal methods.     

含苯并呋喃环的聚苯基单醚喹噁啉

由含苯并呋喃环的芳族四酮与芳族四胺进行溶液缩聚反应，合成了两种新的含苯并呋喃环的聚苯基单醚喹啉，用红外光谱、元素分析、差热及热重分析对聚合物进行了表征，测试了力学性能，并对其在较低温度下形成的多孔薄膜进行了分离、透过性能的研究，实验结果表明，聚合物不仅具有优良的耐热性与力学性能，也具有良好的纯水透过率和截留性能．     

ADSORPTION OF PHENOL AND Pb^2＋ FROM AQUEOUS SOLUTIONS BY A NEW DI-FUNCTION ADSORBENT WITH SULFHYDRYL GROUPS

A new di-function adsorbent （JN-3） was prepared by sulfhydryl modified. Comparing with Amberlite XAD-4 and NDA-150, the equilibrium adsorption for phenol on the JN-3 from aqueous solutions was tested, perfect adsorption capacity was shown. Pb^2＋ can be also removed by JN-3 because of the chelate interaction between sulfhydryl groups and metal ions. This adsorbent could be used in removal of combine pollutants such as phenolic compounds and heavy metal ions from waste streams.     

一种含三氟甲基和呫吨结构聚酰胺的合成与性能

在浓硫酸和3-巯基丙酸催化下,3′-三氟甲基苯基-2,2,2-三氟苯乙酮(1)和甲苯于40～50℃下缩合反应8 h,制得中间体-1,1-二(4-甲基苯基)-1-(3′-三氟甲基苯基)-2,2,2-三氟甲基乙烷(2),继而在光照和N-溴代丁二酰亚胺促进下,将中间体氧化得到二羧酸-1,1-二(4-羧基苯基)-1-(3′-三氟甲基苯基)-2,2,2-三氟甲基乙烷(3),二步反应总收率为77.4%.采用Yamazaki体系,3和9,9-二[(4-氨基苯氧基)苯基]呫吨进行溶液亲核缩聚反应,制得了一种高分子量的(数均分子量为43000,分子量分布为1.8)新型含三氟甲基和呫吨结构的聚酰胺.该聚酰胺为非晶态结构并具有良好的透光率(λcutoff=330 nm),其玻璃化转变温度(Tg)为242℃,在氮气气氛中5%的热失重温度(Td5)为465℃,800℃时的残炭率为50%.聚合物易溶于N,N-二甲基乙酰胺(DMAc)、N-甲基吡咯烷酮(NMP)、间甲酚、吡啶(Py)和四氢呋喃(THF)等有机溶剂中,并可浇注得到韧性好和透明的薄膜,其拉伸强度为85 MPa,拉伸模量为2.0 GPa,断裂伸长率为10%.同时,该聚合物的体积电阻、表面电阻和介电常数分别为2.85×1015Ωcm,4.23×1014Ω和3.55(100 Hz),呈现了良好的电绝缘性能.     

SYNTHESIS,CHARACTERIZATION AND SOLUTION CHEMISTRY OF NEW Re(V) DIOXO COMPLEXES

Abstract

In this work, we report the synthesis, characterization and potentiometric studies of new Re(V) complexes of general formula [ReO₂(amine)₂]⁺ (amine = 1,2-diaminopropane, 1,4-diaminobutane, N,N′-diethylethylenediamine, diethylenetriamine, triethylenetetramine and N-tris(2-aminoethyl)amine). Compounds were prepared starting from [ReO₂I(PPh₃)₂] and characterized by several techniques. The presence of different substituent groups in the diamines (including alkyl and amine groups) allows the presence of pendant arms. When these groups are free amino groups, they can react with acids such as H⁺ and M²⁺ cations and studied by potentiometry. The formation of very stable binuclear species was demonstrated.     

用微波诱导等离子体发射光谱法测定铁及其它一些元素

水溶液样品用超声雾化法雾化经加热后用常规冷凝器和浓H_2SO_4吸收法去溶,然后引入微波等离子体。详细考察了载气流量、微波功率和HCl浓度等实验条件的影响和KCl对谱线的增强作用。测定了一些地质样品中的铁,得到了满意的结果。     

COMPLEXATION OF METAL IONS WITH 3,5-DI-TERT-BUTYL-1,2-BENZOQUINONE-1-MONOOXIME,ESR STUDIES OF RADICAL INTERMEDIATES

Abstract

The possibility of chelate formation of 3,5-di-terf-butyl-o-benzoquinone-1-monooxime with Cu(II), Co(II), Ni(II), Mn(II), Pd(II) metal ions under N₂ and in air have been investigated. It was found that complexation of metals except Cu(II) and Mn(II) was accompanied by formation of various stable radical species under air. The complexation of Co(II) even under N₂ unlike other metal ions, results in the formation of very stable radical species, which are assigned to phenazinyl type radical. ESR examination of reduction of bis(3,5-di-tert-butyl-o-benzoquinone-1-monooximato)M(II) (M = Cu, Pd) with triarylphosphines P(C₆H₄ X)₃ (X = H, m-Cl, m-CH₃, p-Et₂N) reveal the formation of the N-(2′-hydroxy-3,5-di-tertbutylphenyl)-4′,6′-di-tertbutyl-o-benzosemiquinone iminate radical. Finally, ESR spectra of Cu(II), Ni(II), and Mn(II) complexes at 300 and 130 K, as well as reaction of bis(oximato)Ni(II) with PPh₃ have been studied.     

含偶氮苯基侧基聚硅氧烷的合成及光致变色性

含偶氮苯基侧基聚硅氧烷的合成及光致变色性张其震，张静智，王艳（山东大学化学系济南２５０１００）（山东大学环境科学中心济南２５０１００）关键词聚硅氧烷，光致变色，光异构化，量子产率将光致变色性和液晶性化合物结合可得到新的多功能高分子材料，Ｒｉｎｇｅｄｏ...     

镧系元素钨硅杂多配合物异构体的合成及性质

合成了通式为K_(13)[Ln(β_i-SiW_(11)O_(39))_2]·xH_2O(Ln=La,Ce,Pr,Nd,Sm,Gd,Er;β_i=β_1,β_3)的两个系列的β-异构体。通过元素分析、极谱、循环伏安法,UV和VIS光谱、磁化率以及热分析等手段研究了异构体的组成和性质。     

一种主链含光敏基团聚酰亚胺的合成与表征

通过4,4′-二羟乙基查尔酮与1,2,4-苯三酸酐酰氯反应,得到了一种新型的主链含查尔酮的二酐单体,通过二酐和2,2-双(3(-氨基-4(-羟基苯基)六氟丙烷缩聚并高温亚胺化,得到了一种新型的主链含查尔酮,侧链含羟基的光敏聚酰亚胺,并通过1H-NMR、FTIR、GPC及热分析表征了得到的聚酰亚胺的结构和热性能.这种聚酰亚胺在极性溶剂中具有较好的溶解性,并具有较高的热稳定性,在紫外光照射下,能进行[2+2]的环加成反应.     

含羟基（巯基）的叔胺型螯合树脂的合成及吸附性能

含羟基（巯基）的叔胺型螯合树脂的合成及吸附性能倪才华（湖北荆州师范专科学校化学系荆沙４３４１００）徐羽梧（武汉大学化学系武汉４３００７２）关键词螯合树脂，巯基，吸附性能，贵金属已有研究表明：含硫氮的资合树脂对于贵金属离子有优良的吸附性能ｌ’一又Ｎ，Ｎ...     

三溴偶氮溴膦与稀土元素显色反应的研究与应用

研究了新试剂三溴偶氮溴膦（4－BPA－TB）与稀土元素的显示反应。0．96mol.L^-1HNO3介质中，稀土元素与4－BPA－TB的显色反应灵敏度一致。利用此反应性质，测定钢铁中稀土总量获得满意结果。