极性和非极性溶剂在聚乙烯中的无限稀释扩散系数的测定

 气相法研究小分子溶剂与高分子聚合物材料之间的相互作用是一个快速、准确、方便的方法 ,可以测量多种小分子溶剂在聚合物中的溶解、扩散参数。通过气相法测定了 5种小分子溶剂 (正己烷、正庚烷、正癸烷、乙醇和水 )在固定液聚乙烯中的保留时间和半峰宽 ,运用vanDeemter模型进行数据处理 ,得到上述 5种小分子在聚乙烯中的无限稀释扩散系数 ,获得了十分有意义的结果。     

低价钛引起的芳酮肟的反应

在低价钛试剂 (TiCl4/Sm)作用下取代苯乙酮肟发生脱肟反应生成酮 ,而在同样条件下 ,二芳酮肟则生成二芳酮、胺或希夫碱     

极低密度聚乙烯与其它聚乙烯的共混

从结构角度，用ＤＳＣ，ＷＡＸＤ，ＳＡＸＳ研究了聚乙烯（ＰＥ）家族中极低密度聚乙烯（ＶＬＤＰＥ）与其它ＰＥ的互容性．ＨＤＰＥ／ＶＬＤＰＥ是共晶互容的，以其大量无规部分“溶解”了ＨＤＰＥ的结晶缺陷部分，提高了ＨＤＰＥ的Ｔｃ，Ｔｍ，Ｘｃ，结晶峰半高宽变窄，晶胞参数随组成而有最低值．ＶＬＤＰＥ与ＬＬＤＰＥ结构极为相似，ＤＳＣ及ＷＡＸＤ证明其共混物是共晶相容体系．ＬＤＰＥ／ＶＬＤＰＥ的结晶度符合按组成的计算值，但晶胞参数ａ，ｂ以及晶粒尺寸增大，ＤＳＣ上有分别相应于两组份的两个Ｔｍ；ＶＬＤＰＥ的Ｔｃ，Ｔｍ峰高之和高于按组份的计算值，ＬＤＰＥ的Ｔｍ，Ｔｃ则低于计算值．认为是正如ＬＬＤＰＥ／ＬＤＰＥ，ＬＤＰＥ向充满整个体积的ＶＬＤＰＥ中不断填入，以ＶＬＤＰＥ为晶核而结晶，形成相分离的不相容体系．     

Sol-Gel Synthesis of Humidity-Sensitive P2O5-SiO2 Amorphous Films

The sol-gel synthesis of silicophosphate gels using phosphoryl chloride and tetraethoxysilane as molecular precursors is reported and discussed. Gel-derived glasses and films having the molar compositions 10P₂O₅ · 90SiO₂ and 30P₂O₅ · 70SiO₂ have been obtained. The structure of the dried gels as well as the structural modifications that occurs during the transformations in gel-derived glasses are analyzed by Fourier transform infrared spectroscopy (FTIR). It has been found that the evidence of the P—O—Si linkages begins to appear only on the FTIR spectra of the bulk gels heat treated up to 400°C while they are well resolved on the FTIR spectra of the bulk gel samples heated up to 1000°C indicating that at this temperature the transformation in the corresponding gel-derived glasses occurs. The humidity sensitive properties of the gel-films have been evaluated by electrochemical impedance spectroscopy (EIS). The phosphorous content as well as the temperature of the heat treatments strongly affect the sensitivity to RH of the gel-derived films.     

f-Element/crown ether complexes: 21. Conformational changes in metal complexed versus hydrogen bonded benzo-15-crown-5 in the structure of [Y(OH2)3(NCMe)-(benzo-15-crown-5)][ClO4]3·benzo-15-crown-5·CH3CN

Crystalline [Y(OH₂)₃(NCMe)(benzo-15-crown-5)][ClO₄]₃·benzo-15-crown-5-CH₃CN can be obtained by slowly cooling a reaction mixture of Y(ClO₄)₃·n H₂O with benzo-15-crown-5 in a solution of acetonitrile and methanol (3 : 1) from 60°C to room temperature. The crystal structure of this complex has been determined at –150 and 20°C. The complex is triclinic,P . At –150°C the cell parameters area = 11.986(4),b = 12.071(7),c = 16.364(5) Å, = 93.56(3), = 98.68(3), = 109.68(4)°, vol = 2187 ų, andD _calc = 1.61 g cm^–3 forZ = 2 formula units. 3633 independently observed [F _o 5(F _o)] reflections were used in the final least-squares refinement leading to an agreement index ofR = 0.048. The Y(III) ion coordination geometry approximates a tricapped trigonal prism with three water molecules and three benzo-15-crown-5 oxygen atoms forming the prism, with the two remaining benzo-15-crown-5 oxygen atoms and the acetonitrile molecule completing the coordination as capping atoms. The three water molecules hydrogen bond a second crown ether molecule and two of the perchlorate anions. The two acetonitrile molecules have contacts with perchlorate oxygen atoms close enough for some weak interaction. One perchlorate is ordered, one is partially disordered as is the coordinated solvent molecule, and the third anion is totally disordered. The two unique crown ether molecules have distinctively different conformations.For Part 20, see reference [1].     

Preparation of water‐soluble,syndiotacticity‐rich,low molecular weight poly(vinyl alcohol) microfibrils in high yields with the low‐temperature polymerization of vinyl pivalate in tetrahydrofuran and saponification

To prepare water‐soluble, syndiotacticity‐rich poly(vinyl alcohol) (PVA) microfibrils for various industrial applications, we synthesized syndiotacticity‐rich, low molecular weight PVA by the solution polymerization of vinyl pivalate (VPi) in tetrahydrofuran (THF) at low temperatures with 2,2′‐azobis(2,4‐dimethylvaleronitrile) (ADMVN) as an initiator and successive saponification of poly(vinyl pivalate) (PVPi). Effects of the initiator and monomer concentrations and the polymerization temperature were investigated in terms of the polymerization behaviors and molecular structures of PVPi and the corresponding syndiotacticity‐rich PVA. The polymerization rate of VPi in THF was proportional to the 0.91 power of the ADMVN concentration, indicating the heterogeneous nature of THF polymerization. The low‐temperature solution polymerization of VPi in THF with ADMVN proved to be successful in obtaining water‐soluble PVA with a number‐average degree of polymerization (P_n) of 300–900, a syndiotactic dyad content of 60–63%, and an ultimate conversion of VPi into PVPi of over 75%. Despite the low molecular weight of PVA with P_n = 800, water‐soluble PVA microfibrillar fibers were prepared because of the high level of syndiotacticity. In contrast, for PVA with P_n = 330, shapeless and globular morphologies were observed, indicating that molecular weight has an important role in the in situ fibrillation of syndiotacticity‐rich PVA. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1103–1111, 2002     

Design,Synthesis and Bioactivity of Novel Low Bee-Toxicity Compounds Based on Flupyrimin

Neonicotinoids are important insecticides for controlling aphids in agriculture. Growing research suggested that neonicotinoid insecticides are a key factor causing the decline of global pollinator insects, such as bees. Flupyrimin (FLP) is a novel nicotinic insecticide with unique biological properties and no cross-resistance, and is safe for pollinators. Using FLP as the lead compound, a series of novel compounds were designed and synthesized by replacing the amide fragment with a sulfonamideone. Their structures were confirmed by ¹H NMR, ¹³C NMR and HRMS spectra. Bioassay results showed that compound 2j had good insecticidal activity against Aphis glycines with an LC₅₀ value of 20.93 mg/L. Meanwhile, compound 2j showed significantly lower acute oral and contact toxicity to Apis mellifera. In addition, compound 2j interacted well with the protein in insect acetylcholine binding protein (AChBP). The molecular docking on honeybee nicotinic acetylcholine receptor (nAChR) indicated that the sulfonamide group of compound 2j did not form a hydrogen bond with Arg173 of the β subunit, which conforms to the reported low bee-toxicity conformation. In general, target compound 2j can be regarded as a bee-friendly insecticide candidate.     

Effects of Fatty Alcohols with Different Chain Lengths on the Performance of Low pH Biomass-Based Foams for Radioactive Decontamination

Compared with polymers and nanoparticles, fatty alcohols can not only increase the stability of foam, but also maintain better foamability at pH < 2, which is beneficial to reduce waste liquid and increase decontamination efficiency for radioactive surface pollution. However, different fatty alcohols have different hydrophobic chain lengths. The effects of fatty alcohols with different chain lengths on the performance of decontamination foam were studied at pH < 2, to assist in the selection of suitable fatty alcohols as foam stabilizers. Combined with betaine surfactant and phytic acid, biomass-based foams were synthesized using fatty alcohols with different chain lengths. When the hydrophobic tail groups of the fatty alcohol and the surfactant were the same, the foam showed the best performance, including the lowest surface tension, the highest liquid film strength, the greatest sag-resistance and the best stability. However, when the hydrophobic tail groups were different, the space between adjacent surface active molecules was increased by thermal motion of the excess terminal tail segments (a tail-wagging effect), and the adsorption density reduced on the gas-liquid interface, leading to increased surface tension and decreased liquid film strength, sag-resistance and stability. The use of decontamination foam stabilized by fatty alcohols with the same hydrophobic group as the surfactant was found to increase the decontamination rate of radioactive uranium pollution from 64 to over 90% on a vertical surface.     

基于红外隐身及多波段兼容隐身材料

随着探测系统的快速发展和探测精度的提高,隐身技术的需求日益迫切.由于传统的红外隐身材料面临着多途径目标探测的严峻挑战,因此开发既能满足红外隐身要求又能满足雷达隐身、可见光隐身、激光隐身要求的新型兼容隐身材料具有重要意义.红外隐身材料主要针对目标的红外辐射特征进行材料、结构设计,降低目标在背景中热红外辐射信号的突出性以及...     

X波段低副瓣波导缝隙阵列天线特性

:根据Stevenson等效电路法设计了两个X波段低副瓣波导缝隙阵列天线。通过建立多个缝隙时的谐振长度提取模型,计算了存在缝隙间互耦时的谐振长度。两个阵列天线测试结果和仿真结果吻合良好,线阵中心频率实测增益为17.83 dB,其仿真结果为18.2 dB,实测副瓣为-28.12 dB,其仿真结果为-29.97 dB;平面阵列中心频率实测增益为27 dB,其仿真结果为27.9 dB, 实测H面副瓣为-27.2 dB,其仿真结果为-29.9 dB,实测E面副瓣为-22 dB,其仿真结果为-22 dB。