1,4-二(O,O-二乙基硫代磷酰亚胺基)苯的合成及表征

以三氯硫磷与无水乙醇在NaOH存在下合成了二乙基硫代磷酰氯（A）,然后再与对苯二胺反应合成了新型的含磷、氮、硫的膨胀型阻燃剂：1,4-二（O,O-二乙基硫代磷酰亚胺基）苯（B）。利用元素分析、FTIR、1H NMR、MS测试技术表征了化合物B结构,并用热重（TG）和差热分析（DSC）技术研究了其热性能,探讨了反应溶剂及催化剂对反应速率及产率的影响。结果表明,所合成的化合物B的结构与预期的结构一致;热性能研究表明,化合物B在242.2-750℃质量损失为54.39%,1000℃时仍有25.11%的炭残渣,显示出优异的热稳定性和成炭性;在相同反应条件下,用乙腈作为溶剂的反应产率比使用氯仿和二氯乙烷为溶剂的高,并且在合成过程中,单独使用三乙胺作为缚酸剂时产率很低,而当同时加入少量4-二甲氨基吡啶（DMAP）时,产率可达81%。

N-(O,O-二异丙基)磷酰化丝氨酸成肽反应的立体效应研究

研究了 N-( O,O-二异丙基 )磷酰化 -L-(或 D-)丝氨酸和 L-(或 D-)组氨酸在水溶液中的反应及其与 L-(或 D-)组氨酸甲酯在 DMSO中的反应 .用 SDS作对离子试剂 ,采用离子对反相高效液相色谱方法对反应产物进行分析 .结果表明 ,所有反应体系中均有丝组二肽生成 ,而 L-L和 D-D型丝组二肽的生成量约是 L-D和 D-L型产物的

四(O,O-二甲基膦酰基)对苯醌的合成研究

根据Michealis-Arbzov反应,以四氯对苯醌、亚磷酸三甲酯为主要原料,合成了新型阻燃剂四(O,O-二甲基膦酰基)对苯醌,最佳工艺条件为甲苯作溶剂,四氯对苯醌和亚磷酸三甲酯的摩尔比=1∶6,反应时间为6h,反应温度为90℃,产率达90%。并采用红外光谱、核磁共振谱和差热等方法对其结构及性能进行了表征。

Selective depression of galena and chalcopyrite by O,O-bis(2,3-dihydroxypropyl) dithiophosphate

A novel synthesized reagent, O,O-bis（2,3-dihydroxypropyl） dithiophosphate （DHDTP）, was investigated as depressant on the depression of chalcopyrite and galena, when ammonium dibutyl dithiophosphate （DDTP） was used as the collector in flotation tests. Zeta potential and adsorption measurement were performed to study the interaction between depressant and minerals. The flotation tests of two minerals show that DHDTP has slight depression on chalcopyrite in the whole pH range and strong depression on galena in the pH range of 6-10. When DHDTP dosage is increased, the recovery of galena decreases rapidly, while that of the chalcopyrite decreases slightly. The satisfied separation results of artificially mixed samples are that the copper grade and recovery rates of concentrate are 24.08% and 81%, respectively, when the pH is 6 with 278 mg/L DHDTP. Zeta potential and adsorption measurements show that DHDTP has more strongly adsorotion capacity to galena than chalcoovrite.

Catalytic Dechlorination and Kinetics of o-Dichlorobenzene by Pd/Fe

o-Dichlorobenzene (o-DCB) was dechlorinated by Pd/Fe powder in water throughcatalytic reduction. The dechlorination reaction is believed to take place on the surface site ofthe catalyst via a pseuclo-first-order reaction. The final reduction product of o-DCB is benzene.The dechlorination rate increases with the increase of bulk loading of palladium due to the increaseof both the surface loading of palladium and the total surface area. Dechlorination efficiencyaccounts for 90% at Pd/Fe mass ratio 0.02% and metal to solution ratio about 53.3g · L^(-1) in 120minutes. Dechlorination is affected by the reaction temperature, pH, Pd/Fe ratio and the addition ofPd/Fe. E_a is found to be 102.5 kJ · mol^(-1) in the temperature range of 287—313 K.

Effect of Na_(2)O on transition and stability of dicalcium silicate based on sintering process

The phase transition,morphology,stability and pulverization performance of dicalcium silicate(C_(2)S)with different Na_(2)O additions during the high-temperature sintering process were studied using XRD,SEM-EDS,FT-IR,and Raman spectra methods.When the CaO to SiO_(2) molar ratio is 2.0 and the Na_(2)O to SiO_(2) molar ratio is below 0.20,the crystalline calcium silicate compounds includeγ-C_(2)S andβ-C_(2)S.As the Na_(2)O addition increases,the proportion,crystallinity and grain size ofβ-C_(2)S in the sintered products increase,those parameters ofγ-C_(2)S decrease,and the content of amorphous phase increases.Na_(2)O mainly forms solid solutions inβ-C_(2)S and inhibits the transition ofβ-C_(2)S toγ-C_(2)S,resulting in the sintered products unpulverized.The stability of sintered products in alkali solution decreases significantly with the increasing Na_(2)O additions,and theβ-C_(2)S solid solution with Na_(2)O is less stable thanγ-C_(2)S.The mechanism that Na_(2)O affects the transition of C_(2)S as well as its stability was also discussed,which can give actual guidance for the treatment of low-grade alumina-containing resources by the sintering process.

Acid-catalyzed chemoselective C-and O-prenylation of cyclic 1,3-diketones

The chemoselective C-and O-prenylation of cyclic 1,3-diketones was achieved by tuning the prenyl source and catalyst.In the presence of the solid acid Nafion,the coupling of 1,3-cyclohexanediones with isoprene gave C-prenylated 5-chromenones.Alternatively,using prenol as the substrate with the Lewis acid Al Cl3 as the catalyst resulted in the exclusive O-prenylation of 1,3-cyclohexanediones.Notably,the resulting products could easily undergo aromatization to deliver prenylated resorcinols that are otherwise difficult to prepare.Our methodology is highly selective,atom-economical,operationally simple,easily scalable,and has potential applications throughout organic synthesis.

Electropolymerization of O-Phenylenediamine in an Ionic Liquid

Ionic liquid like 1-ethyl-3-methylimidazolium bromine ([EMIM]Br) has been used as electrolyte for the electropolymerization of O-phenylenediamine at glassy carbon electrode by cyclic voltammetry. It is found that poly (O-phenylenediamine) film modified electrode has favorable electrochemical activity in acid solution.

One-dimensional Zigzag Chain Coordination Polymer [Zn(μ-phth)(imi)_2]_∞ Bridged by ο-Phthalato

The reaction of zinc carbonate with o-phthalic acid and imidazole in an aqueous-alcohol solution led to the formation of colorless crystals of [Zn(-phth)(imi)2]∞. Single-crystal X-ray analysis has revealed that the complex crystallizes in a monoclinic system, space group Pn with a = 8.394(2), b = 9.976(3), c = 9.959(3) ? ?= 104.409(4)? V = 807.6(4) ?, Z = 2, C14H12N4O4Zn, Mr = 365.65, Dc = 1.504 g/cm3, ?= 1.544 mm-1, F(000) = 372, the final R = 0.0466 and wR = 0.1171 for 1834 reflections with I >2(I). The complex displays a zigzag infinite chain structure in which each zinc (Ⅱ) center is coordinated by two oxygen atoms and two nitrogen atoms to generate a ZnN2O2 distorted tetrahedral geometry. The neighboring zinc atoms are bridged by the o-phthalate ligand. Each chain is linked by hydrogen bonds with its neighbors to form a three-dimensional coordination polymer.

Hydrophobic intensification flotation:Comparison of collector containing two minerophilic groups with conventional collectors

The surface hydrophobization and flotation of a xanthate−hydroxamate collector toward copper oxide mineral were compared with the combined collectors of xanthate and hydroxamate through water contact angle(WCA)and micro-flotation experiments.The results showed that S-[(2-hydroxyamino)-2-oxoethyl]-O-octyl-dithiocarbonate ester(HAOODE)exhibited stronger hydrophobization and better flotation performance to malachite(Cu2(OH)2CO3)than octyl-hydroxamic acid(OHA)and its combination with S-allyl-O-ethyl xanthate ester(AEXE).To understand the hydrophobic intensification mechanism of HAOODE to malachite,zeta potential,atomic force microscopy(AFM)and XPS measurements were carried out.The results recommended that malachite chemisorbed HAOODE to form Cu—HAOODE complexes in which the hydroxamate—(O,O)—Cu and—O—C(—S—Cu)—S—configurations co-existed.The co-adsorption of HAOODE’s hetero-difunctional groups was more stable than the single-functionalgroup adsorption of OHA and AEXE,which produced the“loop”structure and intensified the self-assembly alignment of HAOODE on malachite surfaces.In addition,the“h”shape steric orientation of the double hydrophobic groups in HAOODE facilitated stronger hydrophobization toward malachite than the“line”or“V”hydrophobic carbon chains of OHA or AEXE.Thus,HAOODE achieved the preferable flotation recovery of malachite particles in comparison with OHA and AEXE.

CRYSTAL STRUCTURE OF μ-[meso-1, 2-BIS(PHENYLSULFINYL)-ETHANE]-(O,O')-BIS[DIPHENYLTIN(Ⅳ) DICHLORIDE]

The title complex is of triclinic system space group P1 with its cell parameters: a = 9. 386(1), b = 9. 412(2), c=11. 549(2)(?), α=97. 91(2), β = 81.70(1), γ= 102. 63(1)°, V= 979.2(?)3, Z = l, Mr = 966. 01, Dx =1. 638 gcm-3, μ(MoKα) = 16. 896cm-1, F (000) = 478, final R = 0. 033 and Rw = 0. 046 for 3424 reflections with I≥3σ(I). The two O atoms of the ligand are bonded to two Sn atoms to form a bridged binuclear species which lies on the crystallographic centre of symmetry situated at the centre of the ethylene C -C bond. The unique Sn atom exhibits a trigonalbipyramidal geometry.

Preparation and microstructure characterization of poly-sialate-disiloxo type of geopolymeric cement

In order to investigate the influence of three key molar ratios （n（SiO2）/n（Al2O3）, n（K2O）/n（Al2O3） and n（H2O）/n（K2O））, a total of nine potassium poly-sialate-disiloxo （K-PSDS） geopolymeric cement matrices were designed according to orthogonal design principle. Subsequently, XRD, ESEM-EDXA and MAS-NMR techniques were employed to further characterize the microstructure of the most fully reacted geopolymeric cement matrix. The experimental results show that n（K2O）/n（Al2O3） has the most significant effect on compressive strength amongst the three ratios. The highest compressive strength （20.1 MPa） can be achieved when n（SiO2）/n（Al2O3）=6.5, n（K2O）/n（Al2O3）=0.8 and n（HEO）/n（K2O）=10.0. The FTIR spectra of nine PSDS geopolymeric cement matrices also indicate that geopolymeric cement matrix with the highest strength is the most fully reacted one and possesses the largest amount of geopolymeric cement products. The microscopic analysis reveals that PSDS geopolymeric cement matrix possesses structural characteristics similar to gel substances in having a wide range of Si endowments, but predominantly the framework molecular chains of Si partially replaced by 4-coordinated Al tetrahedral.

Tuning the O–O bond formation pathways of molecular water oxidation catalysts on electrode surfaces via second coordination sphere engineering

A molecular [Ru(bda)]-type(bda = 2,2’-bipyridine-6,6’-dicarboxylate) water oxidation catalyst with 4-vinylpyridine as the axial ligand(Complex 1) was immobilized or co-immobilized with 1-(trifluoromethyl)-4-vinylbenzene(3 F) or styrene(St) blocking units on the surface of glassy carbon(GC) electrodes by electrochemical polymerization, in order to prepare the corresponding poly-1@GC, poly-1+P3 F@GC, and poly-1+PSt@GC functional electrodes. Kinetic measurements of the electrode surface reaction revealed that [Ru(bda)] triggers the O–O bond formation via(1) the radical coupling interaction between the two metallo-oxyl radicals(I2 M) in the homo-coupling polymer(poly-1), and(2) the water nucleophilic attack(WNA) pathway in poly-1+P3 F and poly-1+PSt copolymers. The comparison of the three electrodes revealed that the second coordination sphere of the water oxidation catalysts plays vital roles in stabilizing their reaction intermediates, tuning the O–O bond formation pathways and improving the water oxidation reaction kinetics without changing the first coordination structures.

Crossed Molecular Beams and Theoretical Studies of the O(~3P)+1,2-Butadiene Reaction:Dominant Formation of Propene+CO and Ethylidene+Ketene Molecular Channels

Detailed understanding of the mechanism of the combustion relevant multichannel reactions of O(3P) with unsaturated hydrocarbons (UHs) requires the identification of all primary reaction products, the determination of their branching ratios and assessment of intersystem crossing (ISC) between triplet and singlet potential energy surfaces (PESs). This can be best achieved combining crossed-molecular-beam (CMB) experiments with universal, soft ionization, mass-spectrometric detection and time-of-flight analysis to high-level ab initio electronic structure calculations of triplet/singlet PESs and RRKM/Master Equation computations of branching ratios (BRs) including ISC. This approach has been recently demonstrated to be successful for O(3P) reactions with the simplest UHs (alkynes, alkenes, dienes) containing two or three carbon atoms. Here, we extend the combined CMB/theoretical approach to the next member in the diene series containing four C atoms, namely 1,2-butadiene (methylallene) to explore how product distributions, branching ratios and ISC vary with increasing molecular complexity going from O(3P))+propadiene to O(3P)+1,2-butadiene. In particular, we focus on the most important, dominant molecular channels, those forming propene+CO (with branching ratio ∽0.5) and ethylidene+ketene (with branching ratio ∽0.15), that lead to chain termination, to be contrasted to radical forming channels (branching ratio ∽0.35) which lead to chain propagation in combustion systems.

Synthesis of novel thionocarbamate for copper-sulfur flotation separation and its adsorption mechanism

As a novel collector, O-isopropyl-N,N-diethyl thionocarbamate(IPDTC) was designed and synthesized for copper-sulfur flotation separation. Density functional theory calculations were performed to investigate the electronic structures of IPDTC. The results showed that IPDTC had higher energy of the highest occupied molecular orbital but lower electronegativity than O-isopropyl-N-ethyl thionocarbamate(Z-200). It was predicted that IPDTC had strong collection ability according to the reaction energy criteria. Flotation results demonstrated that the collecting ability of IPDTC to chalcopyrite and pyrite was stronger than that of Z-200. Then, the flotation mechanism was analyzed by measurements of surface tension, adsorption capacity, XPS, FTIR and zeta potential. These results indicated that IPDTC could reduce the solution surface tension. The adsorption capacity of IPDTC on chalcopyrite was higher than that on pyrite, consistent with the results of the flotation tests. FTIR, zeta potential and XPS results also demonstrated that IPDTC was strongly absorbed on the chalcopyrite surface by formation of Cu—S—C bonds, but showed a weak affinity on the pyrite surface.

Oxidative Dehydrogenation of Butane to Butadiene and Butene Using a Novel Inert Membrane Reactor

The oxidative dehydrogenation of butane to butadiene and butene was studied using a conventional fixed-bed ractor (FBR), inert membrane reactor (IMR) and mixed inert membrane reactor (MIMR). When IMR and MIMR were employed, a ceramic membrane modified by partially coating with glaze was used to distribute oxygen to a fixed-bed of 24-V-Mg-O catalyst. The oxygen partial pressure in the catalyst bed could be decreased. The effect of feeding modes and operation conditions were investigated. The selectivity of C4 dehydrogenation products (butene and butadiene) was found to be higher in IMR than in FBR. The feeding mode with 20% of air mixing with butane in MIMR was found to be more efficient than the feeding mode with all air permeating through ceramic membrane. The MIMR gave the most smooth temperature profile along the bed.

Crystal Structure of O，O－Diethyl－（α－p－Hydroxyphenyl－β－Nitroethyl）phosphonate

The crystal structure of the title compound C_12H_18NO_6P has been determined by X-ray diffraction methods. It belongs to orthorhombic space group Pabc with cell parameters: a=10. 708(5), b=16.151(4), c=17. 615(2) A, V=3046. 4 A￣3, Z=8, D_c= 1. 39 g/cm￣3, F(000)=1280, μ=29. 77cm￣(-1) (CuKα), M_r= 303. 25 ,R=0. 065, R_w= 0. 055. In the molecule, the P atom is coordinated by three O and one C atoms with a distorted tetrahedral configuration.

Chiral Phosphine Ligands Derived fro m Sugars .14 . Crystal Structure of Diphenyl( m ethyl4’,6’-O-benzylidene-3’-deoxy-α- D-altropyranoside-3-)phosphine Oxide

The crystal structure of the title compound, C 26 H 27 O 6P, has been determined by single crystal X ray diffraction analysis. The crystal is orthorhombic with space group P2 12 12 1, a=6.154(4), b=17.199(8), c=22.180(3) , V=2347.6 3, D c=1.32 g/cm 3, F(000)=984, μ=1.5 cm -1 , Z =4, and final R =0.075 and R w =0.080 for 1417 reflections (I≥3σ(I)) . The X ray diffraction analysis revealed that the structure of the title compound s similar to that of its parent phosphine and the pyranose and 4, 6 O benzylidene rings remain distorted chair conformations.

新型膨胀型阻燃剂阻燃聚丙烯的应用研究

以三氯硫磷、无水乙醇、对苯二胺为原料所合成的新型含磷、硫、氮的膨胀型阻燃剂(IFR),1,4-(O,O-二乙基硫代磷酰亚胺基)苯(DTPB)对聚丙烯(PP)进行阻燃,用热重法(TG)和差示扫描量热法(DSC)对阻燃PP的热性能进行了研究,利用氧指数仪测定了阻燃PP的极限氧指数(LOI)值,当阻燃剂含量为28%,LOI值为37.8%,并应用扫描电镜(SEM)对阻燃聚丙烯(FRPP)的残炭结构进行了研究,结果表明,该阻燃剂能够促进PP的成炭性,具有优良的阻燃PP性能。

含膦酸酯官能团离子液体对钢/铝摩擦副的润滑作用研究

合成了3种新型1-(O,O-二乙基膦酰丙基)-3-烷基咪唑六氟磷酸盐离子液体,采用SRV型摩擦磨损试验机评价了所制备的离子液体作为润滑剂对钢/铝摩擦副摩擦学性能的影响,并探讨了其润滑机理.结果表明,所合成的离子液体作为润滑剂对钢/铝摩擦副具有优良的润滑作用,摩擦系数低,抗磨性能优良.表面分析结果表明含膦酸酯官能团的离子液体在摩擦副接触表面形成化学吸附边界润滑膜,从而有效地起到抗磨和提高承载能力的作用.