氟表面活性剂C_8F_(17)SO_2N(C_2H_5)C_2H_4(OC_2H_4)的合成与性能

以全氟辛基磺酰氟为原料,与乙胺在异丙醚中加热反应制得N 乙基全氟辛基磺酰胺,再与2 氯乙醇在加热回流下反应得到N 乙基N 乙醇全氟辛基磺酰胺,随后在碱性条件,加热和带压下与环氧乙烷进行聚合反应,得到表面活性剂C8F17SO2N(C2H5)C2H4(OC2H4)nOH,n=8～9。该活性剂在质量浓度为0.05%时就可将表面张力降至19.2mN/m以下,具有良好的表面活性。运用IR,NMR,DSC,TG等技术对该表面活性剂进行了表征和研究。     

Crystal Structure of Neptunium(V) Phthalate (NpO2)2(OOC)2C6H4·4H2O

The crystal structure of (NpO₂)₂(OOC)₂C₆H₄·4H₂O [rhombic cell: a = 15.937(3), b = 26.922(5), c = 8.020(2) Å, space group Pbcn, Z = 8, V = 3441.0(12) ų, d _calc = 2.988 g cm^{- 3}, CAD4, MoK , graphite monochromator, 2934 independent reflections; R ₁ = 0.0352, wR ₂ = 0.0951] was studied. The structure consists of NpO₂ ⁺ cations, H₄C₆(COO)₂ ^{2 -} anions, and molecules of coordinated and crystallization water. The crystal lattice involves neutral layers [(NpO₂)₂(OOC)₂C₆H₄(H₂O)₃] _n parallel to the {101} plane. The dioxocations in these layers are bonded to each other to form cationic networks [the Np···Np distance is 3.911(1)-4.202(1) Å]. The coordination polyhedra of Np(1) and Np(2) are pentagonal bipyramids (CN 7). The point group of the neptunyl(V) groups is close to D _h. These groups are bidentate ligands in the cation-cation interaction. The Np = O bond lengths are 1.852(6) [Np(1)-O(1)], 1.849(7) [Np(1)-O(2)], 1.845(7) [Np(2)-O(3)], and 1.841(7) Å [Np(2)-O(4)]; the O = Np = O bond angles are 178.6(3)° [O(2)-Np(1)-O(1)] and 177.4(3)° [O(3)-Np(2)-O(4)]. The equatorial plane of the Np(1) bipyramid consists of two oxygen atoms of adjacent Np(2)O₂ ⁺ dioxocations, two water molecules, and a single oxygen atom of the phthalate anion. The equatorial plane of the Np(2) bipyramid consists of two oxygen atoms of adjacent Np(1)O₂ ⁺ dioxocations, two oxygen atom of the phthalate anion, and a single water molecule. The bond lengths in the equatorial plane of the bipyramid lie in the following ranges: Np-Oyl 2.373(7)-2.437(7) Å (average 2.397 Å) , Np-Ophth 2.360(7)-2.474(7) Å (average 2.431 Å), and Np-Owater 2.534(8)-2.558(9) Å (average 2.544 Å). The phthalate anions are tridentate bridging ligands binding neptunium atoms only within a single cationic network.     

N-全氟辛磺酰基聚酰胺环氧氯丙烷树脂的制备及防油性能

己二酸与二乙烯三胺在对甲苯磺酸催化下于155 ℃进行缩聚反应4 h,得聚己二酰二乙烯三胺,将其配制成固含量为20%的N,N-二甲基甲酰胺溶液,再与全氟辛基磺酰氟在60 ℃回流1 h,减压蒸出N,N-二甲基甲酰胺,60 ℃干燥后得N-全氟辛磺酰基聚己二酰二乙烯三胺,然后将N-全氟辛磺酰基聚己二酰二乙烯三胺配制成固含量为25%的水溶液,再与环氧氯丙烷在60 ℃反应2 h,经调pH值,加入一定量水可得到固含量12.5%的目标产物N-全氟辛磺酰基聚酰胺环氧氯丙烷树脂.将目标产物用作纸张表面抗油剂,性能良好.     

Synthesis of Double Uranyl Phthalates of the M4[(UO2)4(μ3-O)2(C6H4C2O4)4] ⋅ nH2O Type with M = NH4, K, and Cs. Crystal Structure of K4[(UO2)4O2(C6H4C2O4)4] ⋅ 3H2O

Double U(VI) phthalates with NH ₄ ⁺ , K⁺, and Cs⁺ ions in the outer sphere were synthesized. The X-ray phase analysis shows that their structures are similar. Single crystals were prepared and the structure of K₄[(UO₂)₄(μ₃-O)₂(C₆H₄C₂O₄)₄] ? 3H₂O was solved. In the [(UO₂)₄O₂(C₆H₄C₂O₄)₄]^4? anions forming the main structural motif, each bridging oxygen atom μ₃-O combines one pentagonal and two hexagonal bipyramids, which, in turn, are combined in centrosymmetrical tetramers. The phthalate ions have coordination capacity equal to 3; each ligand coordinates U(1) in the bidentate fashion via one carboxy group and U(2) in the bidentate fashion to form a planar seven-membered chelate ring.     

Brushite (CaHPO4·2H2O) to octacalcium phosphate (Ca8(HPO4)2(PO4)4·5H2O) transformation in DMEM solutions at 36.5 °C

The purpose of this study was to investigate the transformation of brushite (dicalcium phosphate dihydrate, DCPD, CaHPO₄·2H₂O) powders at 36.5 °C in DMEM (Dulbecco's Modified Eagle Medium) solutions. Two sets of brushite powders with different particle shapes were synthesized to use in the above DMEM study. The first of these brushite powders was prepared by using a method which consisted of stirring calcite (CaCO₃) powders in a solution of ammonium dihydrogen phosphate (NH₄H₂PO₄) from 6 to 60 min at room temperature. These powders were found to consist of dumbbells of water lily-shaped crystals. The second one of the brushite powders had the common flat-plate morphology. Both powders were separately tested in DMEM-immersion experiments. Monetite (DCPA, CaHPO₄) powders were synthesized with a unique water lily morphology by heating the water lily-shaped brushite crystals at 200 °C for 2 h. Brushite powders were found to transform into octacalcium phosphate (OCP, Ca₈(HPO₄)₂(PO₄)₄·5H₂O) upon soaking in DMEM (Dulbecco's Modified Eagle Medium) solutions at 36.5 °C over a period of 24 h to 1 week. Brushite powders were known to transform into apatite when immersed in synthetic (simulated) body fluid (SBF) solutions. This study found that DMEM solutions are able to convert brushite into OCP, instead of apatite.     

Crystal structure of a double Np(V) ammonium propionate, NH4[(NpO2)3(C2H5COO)4(H2O)]·3H2O

The structure of NH₄[(NpO₂)₃(C₂H₅COO)₄(H₂O)]·3H₂O was studied by single crystal X-ray diffraction. The single crystals were prepared by hydrothermal synthesis. In the structure, there are three crystallographically independent Np atoms with different equatorial surrounding. All of them have CN 7; the coordination polyhedron is a distorted pentagonal bipyramid. Each NpO ₂ ⁺ cation is bonded to four other cations, acting simultaneously as a bidentate ligand and a coordination center for two other dioxocations. The cation-cation interactions result in formation of trigonal-hexagonal cationic networks.     

Complexes with substituted 2,5-dihydroxy-p-benzoquinones: The inclusion compounds [Y(H2O)3]2 (C6Cl2O4)3·6.6H2O and [Y(H2O)3]2 (C6Br2O4)3·6H2O

Single crystal of [Y(H₂O)₃]₂ (C₆Br₂O₄)₃·6H₂O and [Y(H₂O)₃]₂ (C₆Cl₂O₄)₃·6.6H₂O were grown in aqueous silicagel. The compounds are in principle isostructural. In Y chloranilate one additional water site is occupied as verified by X-ray single crystal structure analysis. Y³⁺ is nine-coordinated by three water molecules and six oxygen atoms of the bischelating (C₆X₂O₄)²⁻ ions (XCl, Br). The coordination polyhedron is an only slightly distorted tri-capped trigonal prism. The connection of Y³⁺ with the dianions leads to infinite, corrugated layers. The layer stacking yields cage-like cavities in which water molecules are accomodated. Hydrogen bonds interlink adjacent layers. Further hydrogen bonds involve the entrapped water molecules. DSC measurements indicated a complicated dehydration process which caused right at the start destruction of the single crystals.     

Synthesis and crystal structure of a new Np(V) oxalate, Na4(NpO2)2(C2O4)3·6H2O

A new oxalate complex, Na₄(NpO₂)₂(C₂O₄)₃·6H₂O, with the Np:C₂O₄ ratio of 2:3 was synthesized and studied by single crystal X-ray diffraction. In the crystal, the NpO ₂ ⁺ cations and oxalate anions are bound in open networks [(NpO₂)₂(C₂O₄)₃] _n ^4n- parallel to the bc plane. The Na(1) cations are accommodated in large voids of the neptunyl oxalate networks with the formation of crimped mixed-cation layers of the composition [Na₂(NpO₂)₂(C₂O₄)₃] _n ^2n- . The negative charge of the layers is compensated by the Na(2) cations arranged between the layers. The Np atoms have a pentagonal bipyramidal coordination surrounding with the equatorial plane formed by the oxygen atoms of three oxalate anions. The structure contains tridentate-bridging and tetradentate-bridging oxalate anions.     

Zn(C7H7N2O4)2制备及其吸附脱硫性能研究

经过酯交换、水解两步反应制备了有机配体1,3-二乙酸咪唑.利用溶剂热法以硝酸锌为金属源制备了金属-有机框架材料Zn(C7H7N2O4)2,并对其进行了温度优化、时间优化以及反应物比例优化,采用了X射线衍射(XRD)对其进行了表征分析.同时采用以苯并噻吩为模型化合物,在相同条件下进行吸附脱硫效果评价.实验结果表明:M-2/T-120/t-72显示出最佳的吸附脱硫性能.     

Complexes with aromatic carboxylic acids II preparation and crystal structure of Cu[C10H4(COO)2(OCOCO)] · 4H2O (1)

Single crystals of Cu[C₁₀H₄(COO)₂(OCOCO)] · 4H₂O were grown in aqueous silicagel. Cu²⁺ is mainly coordinated by two water molecules and two oxygen atoms of the [C₁₀H₄(COO)₂(OCOCO)]²⁻ ions in a square-planar fashion. The coordination sphere is completed by two longer Cu-water distances, thus yielding an elongated octahedron. The main feature of the crystal structure is a binuclear cluster made up of two of these octahedra sharing a common edge and being held together by two bridging [C₁₀H₄(COO)₂(OCOCO)]²⁻ ions. These binuclear units are interlinked to a three-dimensional network by an extensive system of hydrogen bonds involving all water molecules. Bond lengths in the dianion correspond to a system of strongly delocalized γ-electrons with a locally varying degree of partial double bonding.     

非线性光学晶体MnHg(SCN)4(C2H6SO)2的热学和光学性质的测定

制备了一种新型非线性光学晶体二甲亚砜合硫氰酸汞锰(分子式MnHg(SCN)4(C2H6SO)2,简称MMTD).用热重法、差热分析法、差示扫描量热法、热机械分析法、分光光度法和红外光谱研究了它的热学和光学性质.MMTD晶体具有较好的物理化学稳定性.在27℃时,它的比热为699.5 J/mol·℃.晶体的热膨胀系数为α1=5.33×10-5/℃,α2=4.51×10-5/℃,α3=3.10×10-5/℃.MMTD晶体的截止波长为375nm;透光波段为375-2560 nm.MMTD晶体在标准紫光波长404nm的透过率为44.18%,高于硫氰酸汞锰(MMTC)晶体.     

Complexes with substituted 2,5-dihydroxy-p-benzoquinones: AE[C6(C2H5)2O4]·3H2O (AE=Ca,Sr, Ba)

Single crystals of AE[C₆(C₂H₅)₂O₄]·3H₂O belonging to space group P2₁2₁2₁ were grown in aqueous silicagel (AE=Ca, Sr) and in aqueous solution (AE=Ba), respectively. AE²⁺ is coordinated by four oxygen atoms of two bis-chelating [C₆(C₂H₅)₂O₄]²⁻ ions, thus forming infinite, corrugated chains extending along [010]. The coordination polyhedron is completed by additional water molecules. The coordination sphere is different for the three different AE²⁺ ions yielding CN increasing from Ca²⁺ to Ba²⁺. The principle features of the crystal structure, however, remain unchanged. Adjacent chains are interlinked by hydrogen bonds between water molecules of the coordination sphere and the oxygen atoms of the [C₆(C₂H₅)₂O₄]²⁻ ion.     

A single crystal X-ray diffraction study of Na4(UO2)4(i-C4H9COO)11(NO3)·3H2O

Synthesis and the results of IR and single crystal X-ray diffraction study of Na₄(UO₂)₄(i-C₄H₉COO)₁₁·(NO₃)·3H₂O are reported. The crystals are monoclinic; the unit cell parameters at 100 K are as follows: a = 13.697(2), b = 20.285(3), c = 15.991(3) Å, β = 103.760(3)°, space group P2₁, Z = 2, R = 0.0650. The uraniumcontaining structural units are mononuclear moieties [UO₂(i-C₄H₉COO)₃]^? and [UO₂(NO₃)(i-C₄H₉COO)₂]^?, belonging to crystal-chemical group AB ₃ ⁰¹ (A = UO ₂ ²⁺ , B⁰¹ = i-C₄H₉COO^? and NO ₃ ^? ) of uranyl complexes. The IR data are consistent with the results of the single crystal X-ray diffraction study. The influence of the carboxylate ligand volume on the structure of Na[UO₂L₃]·nH₂O crystals (L = acetate, n-butyrate, isovalerate ion) is analyzed.     

无表面活性剂全氟聚醚基磁流体的开发研究

通过巯基-烯烃的点击反应将全氟辛基乙烯接枝到Fe_3O_4@SiO_2-SH表面,得到一种可自分散到全氟聚醚油中的磁性纳米微粒,最终形成无表面活性剂的全氟聚醚基磁流体。采用傅里叶变换红外光谱仪、X射线衍射仪、透射电镜和振动样品磁强计对所得磁性复合材料进行表征。并将此磁流体置于离心机中以3000r/min的转速,离心10min,测定其稳定性。结果表明:最稳定磁流体的磁性微粒的合成条件为:反应温度40℃,氨水用量4.00mL,Fe~(2+)/Fe~(3+)=1.5∶2(摩尔比),TEOS用量3.00mL,3-巯基丙基三甲氧基硅烷用量1.00mL。用该磁性微粒配制的磁流体在离心条件下无明显分层现象,稳定性最高。     

Crystal Structure and Electronic Absorption Spectrum of Double Neptunium(V) Phthalate Co(NH3)6NpO2[(OOC)2C6H4]2·2H2O

Single crystals of Co(NH₃)₆NpO₂[(OOC)₂C₆H₄]₂·2H₂O were grown. The crystal structure of this compound [monoclinic cell: a = 7.748(2), b = 23.051(5), c = 14.608(3) Å, = 96.21(3)°, space group P2₁/c, Z = 4, V = 2593.7(9) ų, d _calc = 2.034 g cm^{- 3}, CAD4 automatic diffractometer, MoK , graphite monochromator, R ₁ = 0.041 for all 3567 reflections observed, wR ₂ = 0.1344 for all 4445 unique reflections, 325 refined parameters] was studied. The structure consists of infinite anionic chains {NpO₂[(OOC)₂C₆H₄]₂} _n ^{3 n -}, [Co(NH₃)₆]^{3 +} cations, and molecules of crystallization water. Neptunium(V) atom is in pentagonal-bipyramidal oxygen surrounding (CN 7); the neptunyl(V) group is linear and symmetrical; the Np = O bond lengths are 1.830(6) and 1.833(5)Å, the O = Np = O angle is 176.4(2)°. The equatorial plane of the bipyramid is formed by five oxygen atoms of phthalate anions. The Np-Oeq bond length correlates with the denticity of the phthalate anions. Two types of phthalate anions are localized in the structure. The first tridentate ligand is a bridge between Np(V) atoms in the chains. The second ligand is coordinated to Np in the bidentate fashion to form NpOCCCCO seven-membered chelate ring. The cation [Co(NH₃)₆]^{3 +} has an octahedral structure. The average Co-N distance in the octahedron is 1.961 Å the N-Co-N bond angles are close to 90°. Two water molecules along with [Co(NH₃)₆]^{3 +} cations are located between the anionic chains {NpO₂[(OOC)₂C₆H₄]₂} _n ^{3 n -}. The chains are additionally bonded along the Z-axis of the crystal by O_w-H···O hydrogen bonds.     

Optoelectronic operation in ferroic [NH2(C2H5)2]2CuxCo1−xCl4 nanocomposites

The complex studies of optically induced piezooptics and second harmonic generation (SHG) are performed for the [NH₂(C₂H₅)₂]₂Cu_xCo_1?xCl₄ nanocomposites in a form of films and bulks. The corresponding nanoparticles (NP) were embedded into different polymer matrices with content of NP varying from 1 % up to 9 % in weight units. The changes of the photoinduced optical SHG were caused by simultaneous illumination of two bicolour coherent laser beams and simultaneously applied dc-electric field at different temperatures, above glass transition temperature. The fundamental 1,064 nm Nd: YAG laser duration was equal to 12 ns. A comparison of the same features with the analogous crystals doped with Fe²⁺ was carried out. The samples doped by Fe³⁺ ions have shown substantially less photo induced SHG up to one order. The time kinetics of the photoinduced changes after the switching off the external laser fields was studied. Temperature dependences of the piezooptics and the SHG near the incommensurate phase existence were explored.     

Sintering of 6H(α)-SiC and 3C(β)-SiC powders with B4C and C additives

The sintering behavior of three fine industrial SiC powders (two 6H()-type and one 3C()-type) has been comparatively investigated. The powders were pressureless sintered with B₄C and C additives between 1950°C and 2250°C in a high temperature dilatometer with flowing Ar atmosphere. The densification and shrinkage rate curves, polytype content, and grain growth were correlated with physical and chemical characteristics of starting powders. One of 6H()-type powders presented good sinterability only after extensive milling, even though it presented small average particle size, narrow particle size distribution and high specific surface area. The main difference in densification behavior among powders was the narrower shrinkage rate curve of -SiC powder, with its maximum shifted to higher temperature. Grain growth and phase transformation simultaneously occurred. In -SiC, 6H polytype partially transformed to 4H. This transformation was favored by aluminum impurity and resulted in a microstructure with more elongated grains. In -SiC, 3C transformed mainly to 6H, 15R and 4H, introducing many stacking faults which resulted in elongated SiC grains.     

硫丹等十种持久性有机污染物进入淘汰“黑名单”

正在北京召开的"中国斯德哥尔摩公约国家实施计划更新启动会"上,环境保护部副部长翟青宣布,从即日起,《公约》修正案对我国生效。即在10年内,我国将全部淘汰硫丹、全氟辛基磺酸及其盐类和全氟辛基磺酰等10类新增持久性有机污染物。据悉,这十类新增物质中,我国从未生产和使用十氯酮、六溴联苯、六溴二苯醚和七溴二苯醚3类物质;α-六氯环己烷、四溴二苯醚等5类物质在我国曾有过生产和使用,但目前已停止了生产和使用。硫丹、全氟辛基磺酸及其盐类和全氟辛基磺酰氟2类物质在我国还有生产和使用。     

SiH4／C2H4体系激光合成SiC超细粉

本文报道了ＳｉＨ４／Ｃ２Ｈ４体系激光合成ＳｉＣ超细粉研究及对合成的ＳｉＣ超细粉进行的ＴＥＭ（ＴＥＤ）、ＸＲＤ、ＦＴＩＲ、ＸＰＳ及Ｒａｍａｎ散射等测试分析。在部分样品中发现了ＳｉＣ空心颗粒，讨论了ＳｉＣ超细粉的成核成长规律，得出了一些有价值的新结果：ＳｉＣ超细粉的合成由Ｓｉ成核生长和碳化组成；反应温度较高时，为获得接近化学计量化的ＳｉＣ超细粉，要求有较高的源气Ｃ／Ｓｉ比，并且高的Ｃ／Ｓｉ比有利于降低     

无水型双(全氟丁基磺酰)亚胺锂的合成与表征

以全氟丁基磺酰氟为原料,经胺化、成盐、中和、置换反应合成了无水型双(全氟丁基磺酰)亚胺锂。优化了双(全氟丁基磺酰)亚胺三乙胺盐的合成条件。较优的条件为:n(C4F9SO2NH2)∶n(C4F9SO2F):n(NEt3)=1:1.04:1.4,反应温度80℃,反应时间42h。在该条件下,反应收率可达99%以上,合成双(全氟丁基磺酰)亚胺锂的总收率为53.3%。通过FT-IR、1 H-NMR、MS和ICP等对中间体及最终产物进行了表征。