聚有机硅丙烯酸酯/蒙脱土纳米复合乳液的流变性

本文采用原位插层聚合的方法,单体插层插入有机蒙脱土片层中,然后引发原位聚合,制备了聚有机硅丙烯酸酯与有机蒙脱土的复合乳液。并用旋转粘度计对其流变性进行了研究。发现乳液的表观粘度(ηa)、稠度系数(K)、零剪切粘度(η0)、粘流活化能(Ea)随有机硅含量增加而增加,而流动指数(η)则减小;ηa、K、η0、Ea随有机蒙脱土含量的增加先增大后减小,当蒙脱土含量为1％时达最大值,n则为最小值。     

双单体原位接枝插层法制备聚丙烯纳米复合材料的研究Ⅰ.制备、表征及力学性能的研究

用有机插层剂处理蒙脱土原土 ,制得有机蒙脱土 (O MMT) .采用双单体 (马来酸酐和苯乙烯 )原位接枝插层法 ,制备了聚丙烯 蒙脱土纳米复合材料母料 .将母料与聚丙烯基体在双螺杆上共混挤出 ,制得聚丙烯 蒙脱土纳米复合材料 (PP Montmorillonetenanocomposites,PMNC) .这是制备聚合物纳米复合材料的一种新方法 .通过X 射线衍射测试 (XRD)表明 ,有机蒙脱土片层 0 0 1面间距从原土的 1 4 9nm扩大到 2 96nm ,复合材料中蒙脱土片层 0 0 1面间距由有机蒙脱土的 2 96nm扩大到 4 0nm .力学性能测试表明 ,复合材料的力学性能明显优于PP基体 ,在提高材料拉伸强度的同时 ,缺口冲击强度也得到很大的提高 .用扫描电镜 (SEM)对材料的冲击断面形貌进行了研究 ,并从理论上分析了断裂机理 .随着蒙脱土含量的增加 ,冲击断裂形式逐渐从脆性断裂变成韧性断裂     

聚苯乙烯/硅烷偶联剂修饰蒙脱土纳米复合材料的制备与表征

用硅烷偶联剂修饰蒙脱土，制备了聚苯乙烯/蒙脱土纳米复合材料，并用XRD、FTIR、TEM和TGA等对样品进行了表征，发现硅烷偶联剂对蒙脱土表面进行了良好的修饰；苯乙烯单体在蒙脱土层间的聚合导致蒙脱土片层剥离并无规分散在聚合物基体中，片层长度为100-200nm，厚度小于10nm。     

丙烯酸-丙烯酰胺原位插层共聚制备高吸水性蒙脱土纳米复合材料的研究

在钠基蒙脱土(MMT)悬浮液中，采用丙烯酸(AA)和丙烯酰胺(AM)两种单体进行原位插层共聚，得到高吸水性纳米复合材料。研究了引发剂和交联剂对材料吸水率的影响。X射线衍射(XRD)结果表明：复合材料中蒙脱土片层001面的层问距随mMMT／mM的减小而增大，当mMMT／mM≤1／3时，复合材料中的蒙脱土已完全剥离。DSC测试表明，在蒙脱土含量较低时，其玻璃化转变温度Tg随MMT含量的升高逐渐提高。吸水速率和保水能力测试结果表明，材料吸收去离子水能力达610g／gR，吸收盐水(wNaCl=0．009)能力达89g／gR。蒙脱土片层的引入。在一定程度上提高了材料的初期吸水速率和加压下的保水能力。     

新型茂钛催化剂原位本体聚合法制备间规聚苯乙烯/蒙脱土纳米复合材料

采用多碳氨基酸对蒙脱土进行改性 ,得到改性蒙脱土 (MTN) ,并使其层间距扩大 ,在一定条件下用茂金属催化剂Cp Ti(O C6 H4 F) 3 进行苯乙烯原位聚合发现 ,在氨基酸改性的蒙脱土存在下 ,茂金属催化剂活性有所提高 ,能制得间规聚苯乙烯 (sPS) 蒙脱土纳米复合材料 ,考察了蒙脱土用量对配位聚合的影响及该复合材料的形态结构、热稳定性和结晶性能     

胶乳接枝插层法天然橡胶/蒙脱土/聚丙烯酸丁酯纳米复合材料结构与性能的研究

采用胶乳接枝插层法,引入单体,制备了天然橡胶蒙脱土聚丙烯酸丁酯纳米复合材料.X射线衍射(XRD)和透射电镜(TEM)结果表明,在单体丙烯酸丁酯(BA)的作用下,改性蒙脱土片层被进一步撑大,并在橡胶基体中以纳米级分散;动态粘弹谱(DMA)测定结果显示,该体系的玻璃化温度有所提高,且60℃时具有较低的tanδ值,说明具有较小的滚动阻力;物理机械性能测试表明该方法有效地实现了对天然橡胶的补强.     

高密度聚乙烯/蒙脱土纳米复合材料膨胀阻燃体系的性能

使用以乙烯/醋酸乙烯共聚物(EVA)为相容剂的高密度聚乙烯/蒙脱土(HDPE/OMT)纳米复合材料作为基体,制备了含不同成炭剂的聚磷酸铵(APP)膨胀阻燃体系,对其阻燃性能进行了比较和研究,并分析了蒙脱土与膨胀阻燃剂协效作用的机理。热重分析(TGA)、垂直燃烧(UL-94)、极限氧指数(LOI)、锥形量热计结果表明:APP/季戊四醇(PER)体系熔融过程较短可形成蒙脱土增强炭层;PER/PA/OMT体系中较高的有机物含量有利于蒙脱土迁移和堆积。     

丙烯酸树脂／蒙脱土纳米复合材料的制备研究

采用离子交换法,用十六烷基三甲基溴化铵对钠基蒙脱土(Na-MMT)进行改性制备了有机蒙脱土(OMMT).用丙烯酸(AA)、硫酸化蓖麻油、乳化剂OP-10、过硫酸钾为原料进行水溶液聚合制得丙烯酸树脂.将丙烯酸树脂与改性蒙脱土通过聚合插层制备了丙烯酸树脂/ 蒙脱土纳米复合材料.通过傅立叶变换红外(FTIR)和X-射线衍射 (XRD)等手段对复合材料的结构进行了表征,结果表明:丙烯酸树脂插层进入有机蒙脱土内可形成插层型或剥离型的纳米复合材料.蒙脱土含量及蒙脱土与丙烯酸树脂的反应温度、反应时间均对复合材料的剥离行为产生影响,在蒙脱土含量为树脂固含量的7%、温度为70℃、反应4h的条件下可得到完全剥离的纳米复合材料.     

光诱导聚合蒙脱土插层纳米复合材料的研究

用两种光聚合法研究了蒙脱土插层复合材料的制备.用小角X光衍射技术对产物内蒙脱土的结构进行表征,结果表明,蒙脱土经改性后能很好地使聚合单体及预聚物插入黏土层内并在光照下"就地”聚合生成光聚合复合材料.对光聚合法制备蒙脱土纳米复合材料的优缺点进行了初步讨论.     

改性蒙脱土吸附2,4-二氯-5-硝基苯酚的研究

分别采用新型双子阳离子表面活性剂Y-16和十六烷基三甲基溴化铵(CTAB)改性钠基蒙脱土,通过IR、TGA、XRD对其进行表征,研究了表面活性剂的浓度、改性蒙脱土的用量以及接触时间对2,4-二氯-5-硝基苯酚(DCNP)吸附的影响。结果表明:上述两种表面活性剂成功插入钠基蒙脱土层间结构且扩大了其层间距。随着表面活性剂的浓度、改性蒙脱土的用量、接触时间的增加,改性蒙脱土对DCNP的吸附量也随之增加,并达到最大值。当采用0.1g 1.8CEC改性蒙脱土且接触时间为180min时,CTAB-MMT和Y-16-MMT对DCNP达到最大吸附量分别为184.84mg·g~(-1)、164.47mg·g~(-1)。改性蒙脱土对DCNP的吸附行为符合二级动力学方程和Langmuir等温吸附方程。     

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%.     

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.     

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.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

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.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.