Synthesis and Structural Characterization of Triorganotin(IV) Derivatives with 2,2′-Thiodiglycolic Acid and 3,3′-Thiodipropionic Acid

The synthesis and structural characterization of four novel triorganotin(IV) complexes, {(R₃Sn)₂[C₂H₄S(COO)₂]} _n (R = Me: 1), {(R₃Sn)₄[C₂H₄S(COO)₂]₂} _n (R = nBu: 2), {(R₃Sn)₂[C₄H₈S(COO)₂]} _n (R = Me: 3; nBu: 4) were obtained by the reaction of 2,2′-thiodiglycolic acid, 3,3′-thiodipropionic acid and the corresponding R₃SnCl (R = Me, nBu) with potassium hydroxide in methanol. All the complexes were characterized by elemental analysis, Fourier transform infrared and nuclear magnetic resonance (¹H, ¹³C, ¹¹⁹Sn) spectroscopies, X-ray crystallography and thermogravimetric analyses. The crystal structures show that 1 has 2D network structure in which 2,2′-thiodiglycolic acid acts as a tetradentate ligand coordinating to the trimethyltin(IV) ions. Complexes 2, 3, and 4 are 3D metal-organic framework structures in which the deprotoned acids act as a tetradentate ligand afforded by four oxygen atoms.     

Synthesis of soluble polyarylenes containing alternating 4,4′-(1,1′-binaphthyl) and 4,4′-(3,3′-diphenyl)biphenyl structural units

Summary The synthesis and Ni(0) catalyzed homocoupling polymerization of 4,4-bis[5-(trifluoromethanesulfonyloxy)-2-biphenylyl]-1, 1-binaphthyl (9) are described. This polymerization reaction produces a soluble polyarylene containing alternating 4,4-(1,1-binaphthyl) and 4,4-(3,3-diphenyl)biphenyl structural units.     

Coordination of cobalt(III), nickel(II), copper(II), palladium(II) and platinum(II) with N-ethyl-N′-(4′-methylthiazol-2′-yl)thiourea (HL)

Coordination complexes of formula [ML₂], [CoL₃], [Pd(HL)Cl₂], [CuLCl(H₂O)] and [CuL₂(H₂O)₂] {L=anion of N-ethyl-N^′-(4^′-methylthiazol-2′-yl)thiourea; M=Pt^II, Pd^II or Ni^II} were prepared and characterized by elemental analyses, magnetic susceptibilities, and by IR, NMR, electronic and mass spectral measurements.     

Extraction of Uranium(VI) and Thorium(IV) from Nitric Acid Solution by N,N,N′,N′ – Tetraoctylglutaricamide

Synthesis and characterization of N,N,N′,N′-tetraoctylglutaricamide (TOGA) was carried out and used for extraction of U(VI) and Th(IV) from nitric acid solutions. The processes of extraction were determined by the slope analysis and by analyzing a function that allows the simultaneous treatment of all the experimental points obtained in different conditions. The different factors affecting the extraction distribution ratio(D) of U(VI) and Th(IV) (extraction concentration, concentrations of nitric acid, salting-out agent NaNO₃ concentration, equilibration time, temperature, and types of diluents) were investigated. The results obtained indicated that the extraction species of U(VI) and Th(IV) are mainly extracted as UO₂(NO₃)₂·1.0TOGA and Th(NO₃)₄·1.5TOGA. The apparent equilibrium constant of U(VI) and Th(IV) extraction determined are 3.35 ± 0.03 L³/mol³ and 1.87 ± 0.01 L⁵/mol⁵ at 298 ± 1 K. Thermodynamic parameters such as the free energy(ΔG), enthalpy(ΔH), and entropy(ΔS) changes associated with the extraction processes could be evaluated. Back-extraction of U(VI) and Th(IV) from organic phases was also studied.     

直接光度法测定印染废水中铈(IV)

在硫酸溶液中,铈(IV)的强氧化性对间甲酚紫有褪色作用,其褪色程度与铈的浓度有关,据此建立了直接光度法测定痕量铈的新方法。考察了各种实验条件对灵敏度的影响。结果表明,最佳实验条件为:硫酸1.3 m L,间甲酚紫1.4 m L,反应温度80℃,加热反应时间10 min。线性范围为0~6μg/m L,检出限为0.046μg/m L。可用于印染废水中铈的测定。     

改性高岭土上甲苯的选择性硝化(IV)

应用Ｍｅｎｋｅ条件，在改性高岭土固体酸催化下，甲苯能被浓硝酸对位选择性硝化，表现在对邻硝化产物比例达到１．５。     

直接光度法测定印染废水中铈(IV)

在硫酸溶液中,铈(IV)的强氧化性对间甲酚紫有褪色作用,其褪色程度与铈的浓度有关,据此建立了直接光度法测定痕量铈的新方法。考察了各种实验条件对灵敏度的影响。结果表明,最佳实验条件为:硫酸1.3 m L,间甲酚紫1.4 m L,反应温度80℃,加热反应时间10 min。线性范围为0⁶μg/m L,检出限为0.046μg/m L。可用于印染废水中铈的测定。     

2,2′‐(Methylimino)bis(N,N‐dioctylacetamide) (MIDOA), A New Tridentate Extractant for Technetium(VII), Rhenium(VII), Palladium(II), and Plutonium(IV)

2,2′‐(Methylimino)bis(N,N‐dioctylacetamide) (MIDOA) was developed as a new extractant for technetium. MIDOA has a similar backbone to TODGA, N,N,N′,N′‐tetraoctyldiglycolamide, where the nitrogen atom bearing a methyl group replaces the ether oxygen in TODGA. MIDOA is highly lipophilic and ready to use in the HNO₃–n‐dodecane extraction system. The distribution ratio (D) for Tc(VII) is extremely high. In addition, Cr(VI), Re(VII), Mo(VI), W(VI), Pd(II), and Pu(IV) are well extracted by MIDOA. MIDOA has high selectivity toward certain oxometallates. The D(Tc) values decrease gradually with HNO₃, H⁺, and NO₃ ^? concentrations, and the log D vs log [MIDOA] dependence indicates the species extracted to be the 1:1 metal‐ligand complex. It is clear that MIDDA [2,2′‐(methylimino)bis(N,N‐didodecylacetamide)] and IDDA [2,2′‐(imino)bis(N,N‐didodecylacetamide)], which have structures analogous to MIDOA, have similar extraction behavior to that of MIDOA.     

4,4′-(4,4′-砜基二苯氧基)二苯甲酰氯(SODBC)的合成

以对甲基苯酚、4,4′-二氯二苯砜为原料,通过亲核取代反应合成了4,4′-二(4-甲基苯氧基)二苯砜,用高锰酸钾将甲基氧化得到4,4′-(4,4′-砜基二苯氧基)二苯甲酸(SODBA),后者在二氯亚砜和路易斯碱的催化下合成了4,4′-(4,4′-砜基二苯氧基)二苯甲酰氯(SODBC)白色固体.用FT-IR、1H-NMR、13C-NMR、DSC等对其进行了表征,实验证明该化合物具有预期的结构和较高的纯度.     

HEDP与Ge(IV)固体配合物的研究

在常规条件下合成了1-羟基乙叉-1,1-二膦酸(简称HEDP)与Ge(IV)的固体配合物。用元素分析和热分析确定了配合物的组成为:Ge2(OH)4L·3H2O(Ⅰ),L=CH3C(OH)(PO3)2。用红外光谱和热分析对配合物的结构及热稳定性作了较系统的研究。     

4,4′-二苯基甲烷二异氰酸酯(MDI)

生产现状:MDI是聚氨酯的主要原料之一,由于受世界性建筑优势的推动和纯MDI基料新用途的出现,MDI牛产获得了迅速发展。1987年世界生产能力为103.4万吨,其中北美40.5万吨、欧洲45.8万吨、亚洲10.9万吨、南美和东欧6.2万吨。1980年世界MDI产量为56.5万吨,1985年达86.6万吨,1980～1985     

炭92′论文题目(续2)

E15对氯化氰在W五e tlerite炭上分解的表面及气相 研究 N。5 .Melntyre等(够1)E17用气相生长带状石墨丝制备带有序尺寸和显微 结构的超细片状石墨 H。Murayama等(535)E一18用夹入硅酸盐或硅酸铝中把的芳香按正离子 合成石墨 B。Maitnoun等‘(538)P一E4催化剂引晶技术对气相生长炭纤雄形成的 影响 T。Kato等(541)P一ES用硝酸和氨改进活性炭 R。J。J。Jansen(544)P一E7热解炭涂层的烧损性质 E。W inkler等(547)P一ES若干沉积参数对热解炭电阻率的影响 W。Kant等临50)P一Eg甲烷热分解期间热解炭在镍粉和钻粉上的 生成 A .E.Kuguc…     

The electrochemical properties of polyaniline derivatives: poly(4,4′-diphenylamine methylenes) and poly(4,4′-diphenylimine methines)

Summary The electrochemical properties of poly(4,4-diphenylamine methylenes) and poly(4,4-diphenylimine methines) were investigated by cyclic voltammetry. A dehydrogenation reaction occured when poly(4,4-diphenylamine methylenes) underwent a electrochemical reaction and transformed to poly(4,4-diphenylimine methines). The fully oxidized poly(4,4-diphenylimine methines) had the electrochemical band gaps of 1.60–1.72 eV, which were found to significantly smaller than those of the fully reduced poly(4,4-diphenylamine methylenes).     

4,4′-双(4′-羟苯基)戊酸合成的研究

研究了以乙酰丙酸(LA)和苯酚为原料,盐酸为催化剂,巯基乙酸为助催化剂合成4,4’-双(4’-羟苯基)戊酸的工艺。考察了助催化剂种类及用量、反应物料配比、反应温度、反应时间和催化剂用量等因素的影响。通过正交试验,优化了合成工艺。试验表明:n(苯酚)∶n(LA)(摩尔比)=4∶1,反应温度60℃,反应时间为45 h,n(HCl)∶n(LA)=4∶1时,最高产率为97.1%。产物结构经红光外光谱、氢核磁谱进行了表征确定为4,4’-双(4’-羟苯基)戊酸。     

A new dual luminescent pillared cerium(IV)sulfate–diphosphonate

A new pillared cerium(IV) sulfate–diphosphonate with formula Ce₂(2H₂O)[(O₃PCH₂)–NC₁₀H₁₈N–(CH₂PO₃)(SO₄)₂] · 6H₂O has been hydrothermally synthesized and its structure has been solved ab initio from laboratory X-ray powder diffraction data.The luminescent and thermal properties of this compound have been preliminarily studied and the encouraging results place it in the field of functional hybrid materials.     

第十届国际化学工程大会(CHISA′90)和第七届国际干燥会议(IDS′90)

CHISA是捷克语中“化学工程、化工装备设计与自动化”的简写,从1962年起每三年举行一次,地点均在捷克。该大会现己成为世界性的最重要和规模最大的化学工程大会之一。本届大会参加者来自51个国家和地区,共1600余人。会议共提交论文1400     

Non-isothermal degradation kinetics of poly (2,2′-dihydroxybiphenyl)

Catalytic oxidative polymerization of 2,2′-dihydroxybiphenyl (DHBP) was performed by using Schiff base polymer-Cu (II) complex and hydrogen peroxide as catalyst and oxidant, respectively. According to size exclusion chromatography (SEC) analysis, the number-average molecular weight (M _n), weight-average molecular weight (M _w) and polydispersity index (PDI) values of poly (2,2′-dihydroxybiphenyl) (PDHBP) were found to be 37,500, 90,000 g mol⁻¹ and 2.4, respectively. The thermal degradation kinetics was investigated by thermogravimetric analysis in dynamic nitrogen atmosphere at four different heating rates: 5, 10, 15 and 20 °C min⁻¹. The derivative thermogravimetry curves of PDHBP showed that its thermal degradation process had one weight-loss step. The apparent activation energies of thermal decomposition for PDHBP as determined by Tang, Flynn–Wall–Ozawa (FWO), Kissenger–Akahira–Sunose (KAS), Coats–Redfern (CR) and Invariant kinetic parameter (IKP) methods were 109.1, 109.0, 110.0, 108.4 and 109.8 kJ mol⁻¹, respectively. The mechanism function and pre-exponential factor were determined by master plots and Criado–Malek–Ortega method. The most likely decomposition process was a D _n Deceleration type in terms of the CR, master plots and Criado–Malek–Ortega results.     

Synthesis and Polymerization of Bismaleimide Derived from 5(6)-amino-1(4′-aminophenyl)-1,3,3′-trimethyl indane

The acid-catalyzed dimerization of α-methyl styrene led to the formation of trimethyl phenyl indane, which on nitration followed by reduction using hydrazine hydrate gave 5(6)-amino-1(4′-aminophenyl)-1,3,3′-trimethyl indane. This aromatic diamine was used to synthesize bismaleamic acid and imidized to yield bismaleimide. The bismaleamic acid was converted to prepolymer directly by imidizing it in refluxing toluene. All the materials synthesized were characterized using FTIR, ¹H and ¹³C NMR. The direct inlet mass spectral characterizations were carried out for bismaleamic acid, bismaleimide and bismaleimide prepolymer. The fragmentation pattern was discussed in detail and the structure proposed was confirmed. The thermogravimetric studies were done for all the materials and kinetic parameters (energy of activation and frequency factor) were calculated using Dharwadkar and Kharkhanavala method. The structural changes occurring in the thermally polymerized bismaleimide and bismaleimide prepolymer were discussed.     

1,3-二(3′-溴苯基)-5-(4′-氯苯基)苯的合成

以苯乙酮、溴素为原料 ,无水三氯化铝为催化剂 ,按n (苯乙酮 )∶n (溴素 )∶n (AlCl3) =1.8∶2 .3∶4.2制得间溴苯乙酮 ,产率为 6 5 % ;间溴苯乙酮与催化剂四氯化硅按n(间溴苯乙酮 )∶n(四氯化硅 ) =1∶1在无水乙醇中经缩合反应制得 1,3 二 (3′ 溴苯基 )丁烯 2 酮 1(A) ,产率为5 2 % ,以此为中间体与对氯苯乙酮在四氯化硅催化下按n(A)∶n (对氯苯乙酮 )∶n (四氯化硅 )=1.0∶1.0∶2 .5经缩合反应 ,合成了 1,3 二 (3′ 溴苯基 ) 5 (4′ 氯苯基 )苯 (B) ,产率为 43%。