非弹性体增韧—聚合物增韧的新途径

本文是一篇关于非弹性增韧方法的综述。文章首先简要回顾了传统的橡胶增韧韧性聚合物材料的机理,然后着重介绍了最近在国外出现的刚性有机填料(ROF)增韧的基本概念、分析方法和增韧的冷拉机理,列举了脆性塑料粒子和韧性基体组成的合金体系的大量实验结果来说明以上内容,最后通过与传统橡胶增韧机理的对比指出非弹性体增韧是不同于后者的一种新增韧方法,并有可能成为制备高强度、高韧性工程塑料的一种新途径。     

刚性有机填料同时增韧增强改性硬PVC韧性体的研究

刚性有机填料(简称ROF)是用作塑料改性剂的刚性有机聚合物,如PS、PMMA、SAN等。实验发现将少许ROF填充到硬聚氯乙烯韧性体中,能使基体的冲击强度和拉伸强度同时提高,获得既增韧又增强的双重效果。克服了传统的弹性体增韧改性损害基体强度的缺陷。     

PVC/MBS/纳米 BaSO4 复合材料的制备及其性能

采用熔融共混法制备聚氯乙烯(PVC)/甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物(MBS)/纳米重晶石(nano-BaSO4)三元复合材料,考察其力学性能和热稳定性能,并用扫描电镜观察冲击断面的形态.结果表明:MBS 与 nano-BaSO4 可协同增韧 PVC;当 MBS、nano-BaSO4 的含量分别为 10%、1%时,材料的韧性和刚性可同时得以改善,其冲击断面表现出典型的韧性断裂特征;热重分析显示添加 1%nano-BaSO4 可显著提高 PVC/MBS 的热稳定性能,其第一降解阶段的初始分解温度和最快分解温度分别提高了 10℃和14℃.     

均分散胶体的研究 V. 锆化合物均分散颗粒的制备

根据部分稳定氧化锆陶瓷(PSZ)的增韧机制,减小陶瓷粉料ZrO_2颗粒的尺寸是提高陶瓷韧性及其它机械性能的关键,因此合成细微ZrO_2粉料的研究开展得十分活跃.韩利成等用液相沉淀法制备尺寸在微米级以下的氢氧化锆颗粒.村濑嘉夫等在H_2O_2存在下升温水解ZrOCl_2溶液,制备ZrO_2超细颗粒.从所发表的透射电子显微镜(TEM)照片看,他们所制得的颗粒形状和尺寸都不均一,而且粘连,恐难以满足烧制高韧性PSZ     

核-壳粒子增韧聚合物的研究进展

核-壳粒子增韧结合了弹性体增韧和刚性粒子增强的优点，将其用于聚合物共混体系中有可能得到比基体树脂更高韧性更好刚性的复合材料。本文综述了相关核-壳粒子的分类、形态、形成机制，以及它们对聚合物基体的增韧机理，并详细阐述了反应性和非反应性聚合物共混体系中原位形成的核-壳粒子形态演化规律及其对共混物力学性能的影响。     

不同应变速率下纳米橡胶颗粒对环氧树脂的增韧特性与机理分析

为了解释不同应变速率下纳米橡胶颗粒对环氧树脂基体的增韧机理,制备了质量分数为6%的纳米橡胶颗粒/环氧树脂复合材料,分别测试了该材料在3种低应变速率(5×10-4s-1,1×10-1s-1,2.5×10-1s-1)和高应变速率下(90 s-1)的I型平面断裂韧性.结果表明,纳米橡胶颗粒在3种低应变速率下可以显著提高环氧树脂的断裂韧性,提高幅度分别为158%,283%和309%.在高应变速率下,纯环氧树脂的断裂韧性由于动态效应而显著升高,然而纳米橡胶颗粒对环氧基体的增韧效果却不明显,增韧幅度仅为2%.由光学显微镜照片可知,随着应变速率的提高,纳米橡胶颗粒/环氧树脂复合材料断口表面的应力发白区域逐渐较少,甚至在高应变速率(90 s-1)下消失.偏光显微镜照片表明,纯环氧树脂与纳米橡胶颗粒/环氧树脂复合材料的裂纹尖端塑性形变尺寸随着应变速率的升高而减小.通过扫描电子显微镜对断口形貌进行分析可知,不同应变速率下纳米橡胶颗粒在环氧基体中空穴增长程度不同,进而导致纳米橡胶颗粒对环氧基体的增韧效果的不同.     

含磷聚芳醚酮颗粒层间增韧碳纤维/双马树脂RTM复合材料

选用一种在RTM双马来酰亚胺树脂(BMI)注射温度下不溶解的含磷聚芳醚酮(P-PAEK)热塑性树脂作为增韧剂,制备层间颗粒增韧碳纤维增强双马来酰亚胺树脂基复合材料.研究了不同热塑树脂含量对树脂浇铸体冲击性能的影响,利用扫描电镜表征了复相体系的微观形貌并分析其增韧机制,并通过层间断裂韧性测试表征了RTM双马树脂基复合材料增韧前后的层间韧性性能.结果表明,当附载热塑颗粒面密度为2 g/m2时,复合材料的I型层间断裂韧性(GIC)为0.54 k J/m2,II型层间断裂韧性(G_(IIC))为1.36 k J/m~2,较未增韧复合材料分别提升约56%和42%.增韧后的复合材料在保持原有力学性能的同时,其冲击后压缩强度(CAI)提升约29%,层间剪切强度达到111.7 MPa.     

橡胶增韧环氧树脂机理的研究

本文研究了固化剂种类、环氧基体平均网链长度和分散相与基体间键合情况对体系韧性等的影响.结果说明,基体平均网链长度是一个更为重要的影响因素.分散相与基体间的化学键合也是重要的.文中对橡胶增韧环氧树脂的机理提出了见解.在交联密度较低的材料中,在橡胶颗粒附近叠加的应力场诱发下发生纵深度较大的断裂过程.分散相与基体间的化学键合增大该应力场强度有利于加大断裂过程区.     

耐高温改性环氧树脂粘接剂的制备及改性机理研究

采用新型固化体系和端羧基丁腈橡作为环氧树脂的改性剂，制备了一种具有耐高温、高强度、韧性好等特点的环氧树脂粘接材料。同 时对改性机理及增韧机理进行了初步探讨。     

橡胶增韧塑料机理

综述了橡胶增韧塑料机理研究的发展与现状,着重探讨了橡增韧机理中有关脆韧转变的定量研究,同时也讨论了分散相的形态参数、界面相容性和韧性测试条件以及分散相与基体的性能等因素对橡胶增韧塑料性能及增韧的影响,最后提出了橡胶增韧塑料研究的发展趋势。     

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.