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。     

增塑盐改性准固态电解质染料敏化纳米晶太阳能电池

实验使用一种增塑性试剂—双（三氟甲基磺酰）亚胺锂改性PEO-PVDF基聚合物电解质设计并制备了一系列不同浓度双（三氟甲基磺酰）亚胺锂[LiN（SO2CF3）2,LiTFSI]改性的PEO基聚合物电解质。在聚合物电解质中LiTFSI起着增塑剂的作用,经其改性后,聚合物电解质的玻璃化转变温度降低,有利于高分子链段运动和离子传输,进而提高离子的电导率。最终对经增塑盐改性的电解质的特性及其所组装的染料敏化纳米晶太阳电池的光电转换性能进行了研究。     

含磷阻燃剂BHPPO的合成与表征

以苯膦酰二氯(PPD)和对苯二酚(HQ)为原料,合成了含磷阻燃剂2-(4-羟苯基)苯膦氧化物(BHPPO),并通过FT-IR、1 H NMR、13C NMR、ESI-MS对该化合物结构进行了表征。合成BHPPO的最佳工艺条件是在氮气保护条件下,n(PPD)∶n(HQ)=1∶2.4,反应物浓度为0.8mol/L,反应温度为130℃,反应时间为10h,其收率为91.73%;并通过热重分析研究了BHPPO的热稳定性能。     

双酚F及其环氧树脂的合成与性能研究

以苯酚、甲醛为原料,草酸催化合成双酚F,未经提纯的双酚F直接制备双酚F环氧树脂,并考察了合成的双酚F环氧树脂的力学性能.在双酚F合成阶段:n(苯酚)/n(甲醛)=10/1,n(甲醛)/n(草酸)=25/1,70℃,反应4h,得到的双酚F收率和选择性达80%以上;在树脂合成阶段:n(NaOH)/n(BPF)=2,70℃,醚化反应5h,闭环反应3h,制得的环氧树脂的环氧值达到0.59,黏度3.5 Pa·s,树脂固化物具有优异的性能.     

双酚F及其环氧树脂的合成与性能研究

以苯酚、甲醛为原料,草酸催化合成双酚F,未经提纯的双酚F直接制备双酚F环氧树脂,并考察了合成的双酚F环氧树脂的力学性能.在双酚F合成阶段:n(苯酚)/n(甲醛)=10/1,n(甲醛)/n(草酸)=25/1,70℃,反应4h,得到的双酚F收率和选择性达80%以上;在树脂合成阶段:n(NaOH)/n(BPF)=2,70℃,醚化反应5h,闭环反应3h,制得的环氧树脂的环氧值达到0.59,粘度3.5Pa·s,树脂固化物具有优异的性能.     

硫酸钙晶须催化合成一缩二乙二醇双甲基丙烯酸酯

以一缩二乙二醇和甲基丙烯酸甲酯为主要原料,酯交换合成一缩二乙二醇双甲基丙烯酸酯.硫酸钙晶须对合成一缩二乙二醇双甲基丙烯酸酯具有高效催化作用,而半水和无水硫酸钙均没有催化活性.考察了甲基丙烯酸甲酯与一缩二乙二醇物质的量比、催化剂用量、阻聚剂用量等因素对收率的影响,得出了最佳反应条件:n(甲基丙烯酸甲酯);n(一缩二乙二醇)=3.5:1,反应温度为回流温度,催化剂硫酸钙晶须、阻聚剂氮氧自由基加入量分别为一缩二乙二醇质量的3%、0.1%.在此条件下合成的一缩二乙二醇双甲基丙烯酸酯的收率大于96.3%,纯度达97%.     

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.     

1，4，5，8-四硝基-1，4，5，8-四氮杂双环[4.4.0]癸烷合成工艺的改进?

为了改进1,4,5,8-四硝基-1,4,5,8-四氮杂双环[4.4.0]癸烷(TNAD)的合成方法,以1,4,5,8-四氮杂双环[4.4.0]癸烷(THAD)为原料,经成盐、硝化两步反应合成出了TNAD,反应总收率为90%,纯度为98.7%。采用红外光谱、核磁共振氢谱及元素分析对产品结构进行了表征。考察了硝化体系、物料比、反应温度、反应时间对硝化反应的影响,确定了最佳的反应条件:n(THAD.4HNO_3):n(98%HNO_3):n(AC_2O)=1:24:15,反应温度为25℃,反应时间为2 h。     

2003年12月份部分有机氟产品市场参考价格

产品名称规格型号产地价格 (元 /吨 )5 氟乳清酸 98%国产 1 60 0 0 0 0含氟丁基磺酰氯≥ 95 %国产 30 0 0 0 0 0聚全氟乙丙烯FEP 1 0 0J/FEP 1 1 0J杜邦 2 4 0 0 0 0聚全氟乙丙烯FEP 1 4 0J/FEP 1 60J杜邦 2 4 0 0 0 0聚全氟乙丙烯FEP 51 0 0J/FED 92 94杜邦 2 4 0 0 0 0聚全氟     

4,4’-二硝基二苯醚的合成工艺研究

用对硝基氯苯一步缩合法合成4,4’-二硝基二苯醚(DNDPE),研究了反应温度、原料配比(包括对硝基氯苯与碳酸钠、亚硝酸钠的摩尔比)、反应时间、溶剂量对DNDPE收率的影响,并用HPLC对目的产物进行分析。结果表明:DNDPE的较佳合成工艺条件为反应温度150℃,n(碳酸钠)∶n(对硝基氯苯)=0.7,n(亚硝酸钠)∶n(对硝基氯苯)=0.8,反应时间7h,n(DMF)∶n(对硝基氯苯)=5,溶剂回收循环利用可行。在该条件下,DNDPE收率可达77.3%。     

固体超强酸SO42-/TiO2-Al2O3的制备及其催化合成冰片

采用溶胶-凝胶法和浸渍法制备了系列SO_4~(2-)/TiO_2-Al_2O_3固体超强酸催化剂,运用XRD、NH_3-TPD、FT-IR、PyFTIR、XPS、SEM等技术手段,研究了复合催化剂材料的结构与性质,初步探讨了固体超强酸SO_4~(2-)/TiO_2-Al_2O_3催化剂的构效关系,得到适宜的催化剂制备条件为:n(TiO_2)/n(Al_2O_3)=1∶2、硫酸浸渍浓度1mol/L、催化剂焙烧温度500℃。考察了物料物质的量比、催化剂用量、反应时间等对催化合成冰片的影响。结果表明,在物料物质的量比为1∶0.4,催化剂用量为α-蒎烯质量的7%,采用程序升温方式(65℃-1h,75℃-4h,90℃-1h)加热的条件下,固体超强酸SO_4~(2-)/TiO_2-Al_2O_3催化剂的催化活性最高,α-蒎烯的转化率高达100%,龙脑的收率高达59.74%,SO_4~(2-)/TiO_2-Al_2O_3固体超强酸催化剂在重复使用6次的条件下,α-蒎烯的转化率均不变,龙脑的收率下降2.99%,催化剂的重复使用性良好。     

Dry sol-gel polycondensation of hydrosilanes to organosilicas catalyzed by colloidal nickel nanoparticles

The dry sol-gel polycondensation at toluene in ambient air atmosphere of p-X-C6H4SiH3 (X = H, CH3, CH3O, F, Cl) to silica p-X-C6H4SiO15 in high yield, catalyzed by colloidal nickel nanoparticles in-situ generated from nickelocene(II), nickel(II) acetate, and bis(1,5-cyclooctadiene)nickel(0), is described. Similar catalytic activities were observed for the catalysts. Similarly, the dry sol-gel polyco-condensation p-X-C6H4SiH3 (X = CH3, CH3O, F, Cl):C6H4SiH3 (9:1 mole ratio) at toluene in ambient air atmosphere of was performed to yield co-silicas (p-X-C6H4SiO1.5)9(p-X-C6H4SiO1.5)1 in high yield using nickelocene. The co-gels with higher molecular weights and TGA residue yield were obtained when compared to the homogels. The highest yield, molecular weight, polydispersity index, and TGA residue yield were obtained for p-Cl-C6H4SiH3. Some degree of unreacted Si-H bonds still remained in the gel matrix because of steric bulkiness. All the insoluble gels adopt an amorphous structure with a smooth surface. A plausible mechanism for the dry sol-gel reaction was suggested.     

A novel high yield method for dry functionalization of carbon nanotubes

A novel and high yield (> 80%) dry method to functionalize (dry functionalization) carbon nanotubes (CNTs) using hydrothermal method, is reported here. The hydrothermal solution was prepared with HNO3, H2SO4 and H2O2 (1:3:2 vol. ratios) and reaction was carried out from 120 to 200 degrees C for 24 h. CNTs (multi wall) were kept in a way to avoid the direct contact with the solution. Treatment above 180 degrees C resulted in better functionalization of nanotubes as observed from Fourier transform infrared absorption spectroscopic (FTIR) measurements. Field emission scanning electron microscopic (FESEM) images showed that after functionalization, the nanotubes are seen with open ends, granular surface, twisted and are joined together. These clearly indicate the destruction of the graphite structure on the surface. This indicates that after treatment, CNTs reactivity has increased at the ends as well as at the side walls. X-ray Photoelectron Spectroscopic (XPS) studies show a shift in the C 1s peak position, increase in O 1s peak intensity and appearance of an N 1s peak.     

High‐Voltage Lithium‐Metal Batteries Enabled by Localized High‐Concentration Electrolytes

Rechargeable lithium‐metal batteries (LMBs) are regarded as the “holy grail” of energy‐storage systems, but the electrolytes that are highly stable with both a lithium‐metal anode and high‐voltage cathodes still remain a great challenge. Here a novel “localized high‐concentration electrolyte” (HCE; 1.2 m lithium bis(fluorosulfonyl)imide in a mixture of dimethyl carbonate/bis(2,2,2‐trifluoroethyl) ether (1:2 by mol)) is reported that enables dendrite‐free cycling of lithium‐metal anodes with high Coulombic efficiency (99.5%) and excellent capacity retention (>80% after 700 cycles) of Li||LiNi_1/3Mn_1/3Co_1/3O₂ batteries. Unlike the HCEs reported before, the electrolyte reported in this work exhibits low concentration, low cost, low viscosity, improved conductivity, and good wettability that make LMBs closer to practical applications. The fundamental concept of “localized HCEs” developed in this work can also be applied to other battery systems, sensors, supercapacitors, and other electrochemical systems.     

High-Safety and High-Energy-Density Lithium Metal Batteries in a Novel Ionic-Liquid Electrolyte

Rechargeable lithium metal batteries are next generation energy storage devices with high energy density, but face challenges in achieving high energy density, high safety, and long cycle life. Here, lithium metal batteries in a novel nonflammable ionic-liquid (IL) electrolyte composed of 1-ethyl-3-methylimidazolium (EMIm) cations and high-concentration bis(fluorosulfonyl)imide (FSI) anions, with sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) as a key additive are reported. The Na ion participates in the formation of hybrid passivation interphases and contributes to dendrite-free Li deposition and reversible cathode electrochemistry. The electrolyte of low viscosity allows practically useful cathode mass loading up to ≈16 mg cm⁻². Li anodes paired with lithium cobalt oxide (LiCoO₂) and lithium nickel cobalt manganese oxide (LiNi_0.8Co_0.1Mn_0.1O₂, NCM 811) cathodes exhibit 99.6–99.9% Coulombic efficiencies, high discharge voltages up to 4.4 V, high specific capacity and energy density up to ≈199 mAh g⁻¹ and ≈765 Wh kg⁻¹ respectively, with impressive cycling performances over up to 1200 cycles. Highly stable passivation interphases formed on both electrodes in the novel IL electrolyte are the key to highly reversible lithium metal batteries, especially for Li–NMC 811 full batteries.     

Polymer Sensitized Quasi Solid-State Photovoltaic Cells Using Derivatives of Polythiophene

Substituted thiophene sensitized, nanocrystalline TiO2-based quasi solid-state solar cells were fabricated by using either poly （3-thiophene acetic acid） （P3TAA） or a copolymer with poly （3-thiophene acetic acid）-poly （hexyl thiophene） （P3TAA-PHT） polymers and copper iodide （Cul） as a hole conducting material together with an ionic liquid 1-ethyl-3-methylimidazolium bis （trifluoromethylsulfonyl） amide and lithium bis （triflu- oromethanesulfone） imide as additives for charge transport promotion. Dramatic enhancements in the cell performances were observed with the additives in Cul. While the cell sensitized with P3TAA generated a short-circuit photocurrent of -1.45 mA.cm^-2, an open-circuit photovoltage of -345 mV with a total power conversion efficiency of -0.3% under simulated full sunlight of 100 mW-cm^-2 （air mass： 1.5）, the cell sensitized with copolymer P3TAA-PHT delivered -0.25% efficiency under the same conditions with -1.23 mA-cm^-2 as photocurrent and -371 mV as photovoltage.     

Characteristics of a Graphene Nanoplatelet Anode in Advanced Lithium‐Ion Batteries Using Ionic Liquid Added by a Carbonate Electrolyte

A Cu‐supported, graphene nanoplatelet (GNP) electrodes are reported a as high performance anode in lithium ion battery. The electrode precursor is an easy‐to‐handle aqueous ink cast on cupper foil and following dried in air. The scanning electron microscopy evidences homogeneous, micrometric flakes‐like morphology. Electrochemical tests in conventional electrolyte reveal a capacity of about 450 mAh g⁻¹ over 300 cycles, delivered at a current rate as high as 740 mA g⁻¹. The graphene‐based electrode is characterized using a N‐butyl‐N‐methyl‐pyrrolidiniumbis (trifluoromethanesulfonyl) imide, lithium‐bis(trifluoromethanesulfonyl)imide (Py_1,4TFSI–LiTFSI) ionic liquid‐based solution added by ethylene carbonate (EC): dimethyl carbonate (DMC). The Li‐electrolyte interface is investigated by galvanostatic and potentiostatic techniques as well as by electrochemical impedance spectroscopy, in order to allow the use of the graphene‐nanoplatelets as anode in advanced lithium‐ion battery. Indeed, the electrode is coupled with a LiFePO₄ cathode in a battery having a relevant safety content, due to the ionic liquid‐based electrolyte that is characterized by an ionic conductivity of the order of 10⁻² S cm⁻¹, a transference number of 0.38 and a high electrochemical stability. The lithium ion battery delivers a capacity of the order of 150 mAh g⁻¹ with an efficiency approaching 100%, thus suggesting the suitability of GNPs anode for application in advanced configuration energy storage systems.     

Preparation of Gd_2O_2S:Pr Scintillation Ceramics by Pressureless Reaction Sintering Method

Fabrication of Gd2O2S:Pr scintillation ceramics by pressureless reaction sintering was investigated. The 2Gd2O3·(Gd,Pr)2(SO4)3·mH2O precursor was made by hydrothermal reaction using commercially available Gd2O3, Pr6O11 and H2SO4 as the starting materials. Then single phase Gd2O2SO4:Pr powder was obtained by calcining the precursor at 750°C for 2 h. The Gd2O2SO4:Pr powder compacts can be sintered to single phase Gd2O2S:Pr ceramics with a relative density of 99% and mean grain size of 30 μm at 1750°C for 2 h ...     

Formation of fluorine for abating sulfur hexafluoride in an atmospheric-pressure plasma environment

In this study, a large amount of toxic and reactive fluorine (F(2)) was produced in the atmospheric-pressure microwave discharge environment by adding additives to abate sulfur hexafluoride (SF(6)). When H(2) was added, the selectivity of F(2) was as high as 89.7% at inlet H(2)/SF(6) molar ratio (R(H2)) = 1. Moreover, the conversion of SF(6) significantly increased from 33.7% (without additive) to 97.7% (R(H2) = 5) at [SF(6)]=1%, and 0.8 kW because the addition of H(2) inhibited the recombination of SF(6). With the addition of O(2), H(2)+O(2) or H(2)O, the selectivity of F(2) was still greater than 81.2%, though toxic byproducts, including SO(2)F(2), SOF(2), SOF(4), SO(2), NO, and HF, were detected. From optical emission spectra, SF(2) was identified, revealing the SF(6) dissociation process might be carried out rapidly through an electron impaction reaction: SF(6)-->SF(2)+4F. Subsequently, F(2) was formed via the recombination of F atoms.     

锂离子电解液/环氧乙烯基酯树脂固态电解质的制备与性能

将具备优良化学稳定性及高电导率的双三氟甲烷磺酰亚胺锂（LiTFSI）溶于1-乙基-3-甲基咪唑双三氟甲磺酰亚胺盐（EMIM-TFSI）离子液体中制成LiTFSI-EMIM-TFSI电解液,加入环氧乙烯基酯树脂（VER）中对其进行改性。结果表明,添加了上述电解液后的锂离子电解液/环氧乙烯基酯树脂（LiTFSI-EMIM-TFSI/VER）体系可通过FTIR检测到离子液体的特征吸收峰。随着电解液含量的增加,LiTFSI-EMIM-TFSI/VER体系的孔隙率逐渐增大,沟壑与片层结构逐渐增多。这一变化有利于锂离子的传导,提高体系的电学性能,同时可在一定程度上改善树脂的塑性和韧性,提高LiTFSI-EMIM-TFSI/VER体系的力学性能。在本实验中,当电解液含量为40wt%时,LiTFSI-EMIM-TFSI/VER体系多功能性得以最好地实现。