蒙脱土硅氧烷双重改性水性聚氨酯

蒙脱土硅氧烷双重改性水性聚氨酯;水性聚氨酯;蒙脱土;硅烷偶联剂;乳液     

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。     

硅烷化聚氨酯复合催化剂的研究

以聚丙二醇、TDI、N-正丁基-γ-氨丙基三甲氧基硅烷和蒙脱土为主要原料,采用原位聚合方法研究了蒙脱土和有机铋化合物对环境友好和储存稳定的硅烷化聚氨酯催化作用.通过滴定法测试了反应体系中异氰酸根(NCO)含量的变化,发现蒙脱土可以催化NCO与OH的反应,且与有机铋化合物具有协同效应,利用在线红外分析仪证实了蒙脱土的催化...     

有机硅/蒙脱土复合改性聚氨酯弹性体的制备和性能

采用先将聚醚三元醇N330与有机蒙脱土(OMMT)研磨,制得N330/OMMT复合物,再将其与有机硅改性聚氨酯的预聚体混合的方法,以二甲硫基甲苯二胺(DMTDA)为固化剂,制备了有机硅/蒙脱土复合改性聚氨酯弹性体,并用FTIR对产物结构进行了表征.XRD和TEM表明,蒙脱土片层被撑开,并分散在基体中;SEM显示,加入蒙脱土后,有机硅与聚氨酯之间的相容性提高;TGA表明,有机硅和OMMT共同改性聚氨酯后,其耐热性比有机硅单一改性聚氨酯有所提高,并在OMMT含量为5 wt％时提高最大;DSC数据表明,在OMMT含量为5 wt％时,有机硅/蒙脱土复合改性聚氨酯弹性体的Tg明显升高.复合改性材料具有良好的表面性能和力学性能,其拉伸强度、断裂伸长率和硬度在OMMT含量为3 wt％时达到最大值.     

蒙脱土改性醇溶型聚氨酯胶粘剂力学性能研究

利用原位聚合法以甲苯二异氰酸酯、聚醚二醇、正己烷为原料合成了聚氨酯预聚体,在扩链剂中加入蒙脱土,制备蒙脱土改性醇溶型聚氨酯胶粘剂。通过对其XRD,SEM,AFM微观表征,测定了胶粘剂的剪切强度、剥离强度及耐水性,研究了胶粘剂结构与性能的关系。XRD测试结果表明有机化蒙脱土在聚氨酯基体中已完全剥离,SEM和AFM表明蒙脱土在聚氨酯基体中的分散均匀与基体过度良好。当有机化蒙脱土含量为4wt%时聚氨酯胶粘剂的力学性能得到了明显的提高,剪切强度、断裂拉伸强度和断裂伸长率分别提高36.75%、76.80%和134.90%,但剥离强度降低了30.76%,同时吸水率降低了17.54%。     

氯硅烷改性蒙脱土的制备与性能

基于氯硅烷与羟基的反应性,用氯硅烷对蒙脱土进行化学改性,FTIR证实硅烷已接枝到了蒙脱土上,WAXD表明,在极性分散剂中,硅烷成功地插层到了蒙脱土的片层间;而在非极性分散剂中,硅烷插层到蒙脱土片层间的量少,测定了蒙脱土阳离子交换容量(CEC),改性后其CEC值大幅度降低,分散性实验表明,由于改性后的蒙脱土颗粒以及片层间的相互作用力得到极大降低,其在水中和甲苯中的分散性更好.     

基于聚醚胺改性的WPU/MMT纳米复合乳液

采用聚醚胺(PEA)对蒙脱土(MMT)进行插层改性,通过离子交换制备了聚醚胺改性蒙脱土(PEA-MMT)。通过傅里叶红外光谱(FT-IR)、X射线衍射(XRD)表征PEA-MMT的化学结构和层间距。通过在水性聚氨酯(WPU)预聚体乳化过程中引入PEA-MMT的方法,制备WPU/PEA-MMT纳米复合乳液,探究了PEA-MMT的引入对WPU的微观形貌、力学性能、吸水性和透氧性的影响。结果表明:PEA-MMT在WPU膜中均匀分散,且呈插层结构;同时PEAMMT的引入有效提高了WPU的力学性能,降低了WPU的吸水率及透氧率。     

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     

聚氨酯弹性体/蒙脱土纳米复合材料的合成、结构与性能

采用插层聚合法合成了综合力学性能优异的聚氨酯 蒙脱土纳米复合材料 .X 射线衍射结果表明 ,蒙脱土以平均层间距不小于 4 5nm的宽分布分散在聚氨酯基体中 .加入 7 5wt%左右的蒙脱土 ,复合材料的拉伸强度高于纯PU基体的 2倍 ,断裂伸长率则高于纯PU基体的 4倍以上 .TGA分析表明 ,聚氨酯 蒙脱土纳米复合材料的热稳定性略有提高     

基于胶束插层方法制备高热稳定性和大层间距有机化蒙脱土

采用不同方法制备了多种有机化蒙脱土,并分别采用X射线衍射仪、红外光谱分析仪、热重分析仪、电感耦合等离子体发射光谱仪、元素分析仪、扫描电子显微镜对产物进行了表征,并提出了有机物插层新方式——胶束插层.结果表明:适量钠基蒙脱土(Na-MMT)、十六烷基三甲基溴化铵(CTAB)和磷酸三苯酯(TPP)在丙酮/水的混合溶剂中进行溶液插层,得到的有机化蒙脱土具有更大的层间距,比单纯采用CTAB的插层效果显著.产物中含有约21.54%的CTAB和17.47±1.05%的TPP,插层机理为CTAB-TPP胶束插层.该有机化蒙脱土的初始热降解温度比单纯CTAB插层蒙脱土最多提高了17.4℃.采用该方法制备的改性蒙脱土既可以进一步提高蒙脱土的层间距,又可以封闭TPP于MMT的片层间,阻止TPP挥发;同时克服季铵盐改性蒙脱土的热稳定性低的问题,得到了层间距大、热稳定性高的有机化蒙脱土,为有机化蒙脱土在高熔点聚合物改性方面提供了条件.     

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.