碳纤维表面酰氯化及其与尼龙6的接枝Ι.接枝方法及复合材料的力学性能

通过碳纤维(CF)表面官能团的酰氯化,采用阴离子接枝反应制备了表面接枝尼龙6(PA6)的碳纤维. SEM观察表明,接枝PA6的CF表面呈粗颗粒状形态. XPS结果表明,CF表面N/C 比例由接枝前的0.030提高到接枝PA6后的0.061. 接枝率达2.1%以上. 接枝PA6的CF增强了CF与PA6复合材料界面的相互作用,剪切强度提高了14%.     

碳纤维的高温氧化动力学模型

碳纤维的高温氧化动力学模型唐龙贵（浙江大学高分子科学与工程研究所,杭州,３１００２７）关键词碳纤维,氧化,动力学,模型碳纤维是一种具有高比强度、高比模量、耐磨、导电等优良性能的骨架材料,是制造高性能复合材料的基础。它在宇航、军事等高技术工业领域得到了...     

加工工艺对气相生长碳纤维填充聚苯乙烯复合体系导电逾渗与动态流变特性的影响

研究了加工工艺对气相生长碳纤维(VGCF)填充聚苯乙烯(PS)复合体系导电逾渗与动态流变特性的影响.结果表明,低转速、短时间混合有利于VGCF形成较为完善的逾渗网络结构,其复合体系逾渗阈值低、导电性能好.使用作者提出的两相模型描述VGCF/PS复合体系的流变特性,发现低转速、短时间(30 r/min、5 min)混合条...     

炭黑填充聚丙烯/尼龙6/玻璃纤维复合材料的制备及表征

以聚丙烯(PP)和尼龙6(PA6)的共混物为基体材料,以导电炭黑(CB)和玻璃纤维(GF)作为填料,通过熔融共混的方法制备了导电复合材料。研究了GF和CB质量分数对复合材料热稳定性、导电性能、力学性能和微观形貌的影响。结果表明:CB粒子选择性分散在PA6中,同时PA6包覆在GF表面,通过具有较大长径比的纤维相互搭接形成连续的网络结构,从而显著降低复合材料的逾渗阈值。在相同CB质量分数下(2%),PP/PA6/GF/CB的表面电阻率相对于PP/PA6/CB体系降低了5个数量级。此外,引入GF后,材料的热稳定性和拉伸强度都有所提高。     

石墨烯基三维导电网络结构储能电极材料的研究进展

设计和构筑有效的三维导电网络结构对于优化储能电极材料的性能具有重要意义.石墨烯独特二维结构所具有的超高电荷传导、极大的表面负载空间和可形成三维孔(层)隙骨架结构等特性为制备多样化的复合电极材料提供了基础.本文介绍了近年来基于石墨烯的三维网络结构复合电极材料的构筑及其在电化学储能(如锂离子电池、锂硫电池)应用中的研究进展,结合本实验室的研究工作,着重介绍了石墨烯基复合电极材料结构设计的科学原理,讨论了几种石墨烯复合结构,并对未来石墨烯复合结构体系的构筑及其应用作了展望.     

超细颗粒填充高密度聚乙烯复合体的导电和流变学性质(英文)

制备了多壁碳纳米管、石墨和碳黑填充高密度聚乙烯(HDPE)复合体,研究了复合体的导电和流变学性质.利用隧道逾渗模型对关键指数分别为4.4、6.4和2.9的三种复合体的"非普适性"导电行为进行了解释.与此同时,考察了颗粒类型和含量,以及剪切速率对复合体流变学性质的影响.结果表明,复合体系的储能模量在低频区出现"第二平台",而复合黏度则表现出强烈的剪切变稀行为,标志着颗粒在聚合物内部发生聚集形成了网络结构.与石墨和碳黑填充复合体相比,具有更高纵横比的多壁碳纳米管填充复合体具有更高的储能模量和复合黏度.基于Guth-Smallwood理论结合有效介近似的G′r分析结果表明,填充HDPE复合体系的流变学逾渗阈值和导电逾渗阈值吻合良好.     

尼龙6/氯化钾复合材料的结晶与性能

通过熔融共混法制备了不同KCl含量下的尼龙6(PA6)/KCl复合材料,采用示差扫描量热仪(DSC)、流变仪、红外光谱(IR)、电子拉伸机等研究了KCl含量对PA6/KCl复合材料结晶行为、流变性能及力学性能的影响,并研究了其受限机制.力学性能研究结果表明,随着KCl含量的增加,PA6/KCl复合材料拉伸强度和冲击强度呈现出先增大后减小的趋势,在KCl含量为3 phr时,复合材料拉伸强度和冲击强度分别达到最大值82.67 MPa和7.34 k J/m~2,较纯PA6分别增加了10.8%和34.68%,动态力学性能测量结果表明,在测量温度范围内,复合材料的储能模量均高于纯PA6,在25℃体系储能模量(G')随KCl含量的增加而增大,复合体系抵抗弯曲变形能力增加,而结晶行为研究结果表明,增加KCl的含量,PA6/KCl复合材料的成核温度、晶体生长温度、熔融温度及玻璃化转变温度均向低温方向移动,成核密度和成核速率也逐渐减小,结晶能力下降,结晶度减小,结晶度由原来25.30%变为19.34%,而结晶诱导时间逐渐增加.流变性能研究结果表明,随着KCl含量的增加,复合体系的零剪切黏度逐渐增加,且所有的体系均呈现出假塑性流体行为,剪切变稀现象越来越明显,特征松弛时间τ_1、τ_2和τ_3逐渐增加,复合体系的松弛机制发生变化.     

碳纤维表面酰氯化及其与尼龙6的接枝Ⅱ、碳纤维接枝复合材料CF/PA6的等温结晶和熔融行为

碳纤维表面酰氯化及其与尼龙6的接枝Ⅰ、碳纤维接枝复合材料CF/PA6的等温结晶和熔融行为;阴离子接枝;碳纤维/尼龙6复合材料     

聚(N-异丙基丙烯酰胺)/聚丙烯酰胺无机/有机互穿网络水凝胶的制备及表征

通过紫外引发聚合方法制备了无机交联的聚(N-异丙基丙烯酰胺)(PNIPAAm)/有机交联的聚丙烯酰胺(PAAm)互穿网络(IPN)水凝胶.利用FTIR和SEM分别表征了凝胶的化学结构和内部形态;测定了凝胶在高温(50℃)时的退溶胀性能;利用DMA和DSC分别研究了凝胶的储能模量随温度的变化及热相转变行为.研究表明,该IPN凝胶具有温度敏感性;与未互穿的无机交联PNIPAAm凝胶相比,IPN凝胶具有多孔的网络结构和超快的响应速率,如10min内失去90%的水;其储能模量增加了3～4倍,相转变行为变弱,而最低临界溶解温度(LCST)提高了1.4℃.     

氧化石墨烯增容尼龙6/聚苯乙烯共混体系的研究

氧化石墨烯(GO)亲水性的边缘和疏水性的中间片层使其具有两亲特性.利用GO的这种特性,将其加入尼龙6(PA6)/聚苯乙烯(PS)的共混体系,以提高PA6和PS的相容性.通过两步法制备了PA6/PS/GO共混物,研究了GO对PA6/PS共混材料结构形态与力学性能的影响,并对其增容机理进行了探讨.扫描电镜(SEM)结果表明,添加GO后,共混材料的分散相尺寸明显变小,分散更为均匀,少量的GO即可达到良好的增容效果.动态力学性能(DMA)测试进一步证明了GO对PA6/PS共混物具有一定的增容性.理论计算也表明PS/GO共混物和PA6具有更接近的表面自由能和较低的界面自由能.添加GO后共混物材料的拉伸性能和韧性明显提高.GO添加量为0.1 wt％时,共混材料的断裂伸长率较未添加GO的共混材料提高了170％,断裂能也提高了近240％.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.