炭黑填充顺丁橡胶(BR)复合材料中多重相互作用的研究

通过溶液浸泡及高速离心的方法分离了填料与聚合物间的强弱相互作用,研究了炭黑填充BR复合材料中多重相互作用与炭黑含量的关系,基于不同结合橡胶含量与储能模量的关系,提出了该多重相互作用随炭黑含量的演变模型.结果表明,存在于炭黑凝胶Ⅰ中的玻璃化转变温度和结晶熔融峰在炭黑凝胶Ⅱ中均完全消失,该现象意味着炭黑凝胶Ⅰ中测得的玻璃化转变及结晶行为只是与炭黑形成弱相互作用的那部分分子链段的贡献.在选用玻璃化转变温度考察炭黑-橡胶相互作用时应综合考虑样品特性以及测试方法.当炭黑含量不高于50 phr时,结合橡胶Ⅱ的含量随炭黑含量的增多呈线性增大,结合橡胶Ⅲ的含量则受炭黑含量的显著影响.炭黑填充橡胶复合材料中的多重相互作用可通过重叠模型进行描述,当炭黑含量分别为25~30phr,50~55 phr以及70~80 phr时,填充复合材料体系中分别存在结合橡胶Ⅲ的重叠层,结合橡胶Ⅲ和结合橡胶Ⅱ的重叠层,以及结合橡胶II的重叠层.     

不同粒径炭黑混合对复合型导电材料PTC性能的影响

研究了炭黑分散效果对具有PTC效应的高密度聚乙烯／炭黑导电复合材料性能的影响。实验结果表明，由不同粒度和比表面积的两种炭黑混合后填充的复合材料同由导电性能较好的乙炔炭黑填充复合材料比较，前者具有较低的渗滤阀值、较高的临界温度、优良的PTC特性以及电阻稳定性好的特点．     

γ－射线辐照对HIPS／SBS共混物结构与性能的影响

采用６０Ｃｏγ－射线对ＨＩＰＳ／ＳＢＳ共混物以不同剂量和时间进行辐照，适当条件下，可改善共混物的性能，其中的丁二烯橡胶相可产生不同程度的交联，使抗张强度、弹性模量增加，热变形温度及硬度明显提高。并观察了交联后形态结构的变化。     

PVC／SBR／MBS三元共混合金的研究

对ＰＶＣ／ＳＢＲ／ＭＢＳ三元共混合金作了研究。在ＰＶＣ／ＳＢＲ体系中加入ＭＢＳ，ＰＶＣ的冲击强度可提高５．５倍，弯曲强度的保留率在８０％左右。电镜和ＤＤＶ测试表明ＭＢＳ的加入提高了ＳＢＲ对ＰＶＣ的相容性，增强了橡胶对ＰＶＣ的界面粘结力。     

γ—射线辐照对HIPS／SBS共混物结构与性能的影响

采用＾６０Ｃｏγ－射线对ＨＩＰＳ／ＳＢＳ共混物以不同剂量和时间进行辐照，适当条件，可改善共混物的性能，其中的丁二烯橡胶相可产生不同程度的交联，使抗张强度，弹性模量增加，热变形温度及硬度明显提高，并观察了交联后形态结构的变化。     

聚乙烯/炭黑复合材料导电体系的结构形态

将导电填料（例如炭黑）加入绝缘的聚合物基体即得到导电复合材料,两组混全物的电阻率随导电填料体积分数的变化而改变,电阻率与导电填料体积分数的关系称为渗流曲线,可分为三个主要区域：低导电填料含量区域,复合材料的电阻率很大,聚合物的电阻率占主导;渗流区域,导电填料含量少量的增加会引起复合材料电阻率很大的提高;高导电填料区域,复合材料电阻率很大的提高;高导电填料区域,复合材料电阻率主要由导电填料的电阻率决定,对于导电复合材料已有大量的实验和理论工作来解释导电复合材料已有大量的实验和理论工作来解释导电填料含量和复合材料各组分的形貌对电性能的影响,其中有效介质普适方程（GEM方程）已经对大量的渗流曲线进行了精确的拟合。聚乙烯／炭黑复合材料中由于炭黑的大量分布很难观测其微观形貌,本文对不同辐照交联程度和不同环境温度下聚乙烯／炭黑复合材料的渗流曲线进行分析,试图找出GEM方程各参数与复合材料各组分形貌的关系,为导电复合材料的设计和制备提供理论基础。     

加工工艺对炭黑填充聚合物双基体复合材料导电性能的影响

制备了炭黑(CB)填充高密度聚乙烯(HDPE)/乙烯-醋酸乙烯酯共聚物(EVA)双基体复合材料,研究了加料顺序、混合时间对复合材料导电性能的影响.结果表明,CB主要分布在HDPE相中;采用CB首先填充EVA然后与HDPE混合,或采用EVA/HDPE共混物与CB混合的加工策略,均可获得导电性较优的导电复合材料.然而,混合过程显著影响CB填充双基体复合材料的导电性.采用EVA/HDPE共混物与CB混合法加工复合材料,导电性受相形态演化影响较小.     

一种新型硅藻土填充橡胶纳米复合材料研究

橡胶的填料问题一直是人们的研究热点,针对炭黑和白炭黑在橡胶生产中存在的污染问题,本文选用成分结构与白炭黑类似的硅藻土来填充各种橡胶。首先对硅藻土进行了改性,并对不同改性剂改性硅藻土用于填充橡胶进行了研究。结果表明2.5份偶联剂Si69的改性效果最佳。通过机械共混法制备了改性硅藻土/橡胶纳米复合材料,通过力学性能测试确定了比较适合硅藻土填充的橡胶是氟橡胶、三元乙丙橡胶和丙烯酸酯橡胶。绿色环保且价格低廉的硅藻土可以替代白炭黑增强填充氟橡胶、三元乙丙橡胶和丙烯酸酯橡胶。     

PVDF-HDPE双相PTC材料的制备、结构与性能

分别以聚偏氟乙烯(PVDF)、高密度聚乙烯(HDPE)为基体,炭黑(CB)为导电填料,采用两步熔融混合法,制备了PVDF-HDPE-CB导电复合材料。通过差示扫描量热(DSC)、溶剂抽提、扫描电子显微镜(SEM)等方法表征了复合材料的结构,采用电阻测试仪等仪器测试了复合材料的性能。研究了PVDF与HDPE体积比与复合材料结构的关系,以及对复合材料导电性、正温度系数(PTC)特性、耐电压性能的影响。结果表明,复合材料具有双相PTC材料结构,在复合材料中,HDPE易形成连续相,少量添加即可显著提高以PVDF为基体的PTC材料的导电性和耐电压性能。     

填充粒子对复合型导电硅橡胶电阻温度特性的影响

研究了炭黑填充复合型导电硅橡胶的电阻温度特性,分析了升温过程中导电硅橡胶电阻特性的详细变化过程。研究了导电粒子和白炭黑含量对导电硅橡胶电阻温度特性的影响,测量了在不同热处理温度下电阻率的变化及加力时电阻的驰豫时间。分析了热处理对电阻特性影响的机理。     

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.