次氯酸钠对硫化橡胶粉表面的氧化改性研究

本文采用次氯酸钠对硫化橡胶粉进行表面氧化改性研究,通过X射线光电子能谱(XPS)、扫描电镜(SEM)、接触角测量对样品进行了表征和分析,并对其最佳工艺条件进行了探究。通过实验表明,氧化剂用量、反应温度及反应时间对胶粉的氧化反应都有影响。其最佳工艺条件的氧化剂用量为40%,反应温度为40℃左右,反应时间为3小时。     

硅烷偶联剂改性纳米氧化锆及其表征

以甲苯为溶剂、硅烷偶联剂为改性剂对纳米氧化锆进行接枝改性。探究了改性剂硅烷偶联剂KH-570的体积百分含量、反应温度和反应时间对纳米氧化锆表面改性接枝效果的影响。采用扫描电镜、能谱分析、傅里叶变换红外光谱(FTIR)、粒径分析等手段表征改性前后纳米氧化锆粉体。结果表明,当硅烷偶联剂KH-570的体积百分含量为10%,反应温度80℃,反应时间30min时,纳米氧化锆表面接枝改性效果最好。此时,硅烷偶联剂KH-570与纳米氧化锆之间形成了化学结合。     

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.     

丙烯酸羟乙酯对硫化胶粉表面的改性研究

本文采用丙烯酸羟乙酯对硫化橡胶胶粉进行表面接枝改性,使胶粉表面部分羟基化.通过X射线光电子能谱(XPS),扫描电镜(SEM),热重分析(TG)对改性粉体进行了测试和表征,探讨了单体用量,引发剂量以及时间的变化对胶粉表面接枝的影响.结果表明,当单体量为20%,引发剂的量为3%,反应时间为6h,接枝改性的效果较好.     

微波处理和溶胶凝胶法共同改性废胶粉及其与天然橡胶复合材料性能的研究

采用微波处理打断废胶粉(WRP)的三维网状结构用来提高WRP在有机溶剂中的溶胀性,然后采用溶胶凝胶法,将微波改性后的WRP浸入正硅酸乙酯中,通过水解反应和缩合反应,在WRP表面原位生成SiO2网络,从而制得改性废胶粉(MWRP).将制得MWRP与天然橡胶(NR)共混,制备了NR/MWRP复合材料,研究了NR/MWRP复合材料的性能.通过热重分析仪、差示扫描量热仪和力学分析表明微波处理最佳时间是20 s.由于微波处理提高了NR与WRP的相容性,原位生成的SiO2粒子起到了补强作用,所以所制备的NR/MWRP复合材料拥有较好的力学性能;随着Si69的加入,抑制了SiO2粒子聚集,提高了SiO2粒子的分散性,从而进一步提高复合材料的力学性能并降低复合材料的Payne效应;在进行频率扫描时,硫化胶的储存模量随频率的增大而增大;硫化胶的温度扫描结果表明,随着温度的升高,复合材料中SiO2粒子聚集程度加剧并且复合材料出现老化的现象.为了提高复合材料的耐老化性能,N,N-间苯撑双马来酰亚胺(BMI)作为一种防老剂加入复合材料中,BMI利用Diels-Aider反应补偿橡胶在老化过程中所损失的交联键并提高NR与WRP的界面相容性,从而提高复合材料的耐老化性能.     

空心微珠的疏油改性对泡沫灭火剂发泡性能的影响

用1H,1H,2H,2H-(十三氟代辛烷基)三乙氧基硅烷(F8261)对空心微珠(HGM)进行表面改性处理,测定了不同条件下油滴在改性空心微珠(MHGM)表面的接触角及停留时间,考察了改性剂浓度、反应时间和反应温度等因素对改性效果的影响,对比了HGM和MHGM对蛋白泡沫液发泡倍数、25%析液时间等参数变化,研究了MHGM对泡沫灭火剂发泡性能和泡沫稳定性的影响.结果表明,在F8261浓度为1.0%,温度为60℃时,超声2.0h,油滴与MHGM的接触角可达132.5°,疏油性能明显增强,灭火剂的发泡性能和油面稳定性显著改善.     

过氧化苯甲酰氧化废胶粉在橡胶沥青中的应用

采用过氧化苯甲酰对废胶粉表面进行氧化改性,并于实验室制备胶粉改性沥青。通过设计3因素3水平正交试验,研究氧化温度、氧化时间及氧化剂用量对改性沥青基本性能指标(针入度、软化点和延度)的影响。对试验结果的极差分析与方差分析表明,氧化温度是影响胶粉改性沥青性能的主要因素,建议氧化改性胶粉的最优反应条件为:氧化温度40℃,氧化时间3.0h,氧化剂用量25g。氧化胶粉改性沥青能使软化点提高到68.2℃,显著改善改性沥青的高温性能。XPS试验结果表明过氧化苯甲酰氧化能使胶粉表面的C—C键和C—H键打开,形成较多的羟基(C—O)和羰基(C=O)等活性基团,显著增加胶粉的表面活性。     

乙醇胺功能化石墨烯及其PVB复合材料的制备

采用乙醇胺对石墨烯进行改性,一步合成了乙醇胺功能化石墨烯(EFG),探讨了实验条件对该过程的影响.结果表明,乙醇胺在对石墨烯进行功能化的同时还能起到还原氧化石墨烯(GO)的作用,反应产物的吸光度随着乙醇胺的用量、反应温度、反应体系pH值和反应时间的增加而增加,而产物中N元素的含量则随之减小,最佳合成条件为:乙醇胺与GO的质量比为4.0,反应温度50℃,体系pH 7.0,反应时间12 h.然后分别采用溶液共混法和原位还原法,制备了两种不同的EFG/聚乙烯醇缩丁醛(PVB)复合材料,研究了EFG的添加量和加入方式对PVB性能的影响.结果表明,EFG的引入可以极大的提高PVB的导电率、紫外线屏蔽能力和力学性能,且采用原位还原法的效果更好.当EFG添加量为3.0 wt%时,复合材料的导电率较PVB升高了约6~7个数量级;当EFG的添加量仅为1.0 wt%时,复合材料对紫外线的屏蔽能力就到达了90%以上.     

胶粉在改性沥青中的物化行为分析

生产胶粉改性沥青(CRMA)是实现废橡胶资源化利用及减轻环境污染的有效途径。为了研究胶粉在沥青中的物理及化学行为,采用邻苯二甲酸二丁酯(DBP)模拟沥青的轻组分,将胶粉置入DBP中,在175℃下,反应1.5 h后分离胶粉与轻组分,对轻组分进行气相色谱与质谱联用(GC-MS)分析,讨论胶粉与轻组分发生的物理化学作用;对不同条件下制备的胶粉改性沥青分离胶粉后进行红外光谱(IR)和差示扫描量热(DSC)分析,研究橡胶改性沥青中的官能团变化和热力学特性。结果表明,分离胶粉后的DBP中存在19种检出物,除含量最高的DBP外,其余物质均为胶粉浸出物或与轻组分的反应产物,即胶粉在轻组分中发生了复杂的物理化学反应。胶粉沥青样品中的—CH_2和C=C双键等特征官能团吸收峰大幅增强,橡胶分子在沥青中发生断链降解释放出小分子物质溶于沥青组分发挥改性作用;195℃、1.5 h和175℃、3.0 h制备的沥青样品DSC谱线出现了强烈的吸热峰,即处理温度过高或时间过长,可能发生胶粉过度降解、胶粉团聚或沥青老化行为,使胶粉改性沥青的物化状态发生改变,导致性能劣化。从胶粉物化变化的角度,建议制备胶粉改性沥青时,胶粉掺量(质量分数)应在20%左右,处理温度不高于195℃,处理时间不超过1.5 h。     

模拟研究石墨烯/生物基尼龙复合材料的界面热阻

生物基尼龙(PA56)源于天然产物,具有优良的环保性能和广阔应用前景,有望替代传统的石油基尼龙材料.为了开发基于PA56的导热材料,利用分子动力学模拟研究方法探索了石墨烯/PA56复合材料界面热阻的影响因素.首先,利用实验测试商用PA56样品的玻璃化转变温度(Tg)和导热系数(Tc),验证了PA56模型的模拟参数.接着,通过设计和比较不同表面改性状态对石墨烯/PA56复合材料的界面热阻的影响规律,最后,为了降低界面改性的难度,设计了一种新型的二嵌段共聚物作为石墨烯/PA56复合体系的界面改性剂,研究了界面改性剂的结构对界面热阻的影响规律.研究结果对于实验研究制备生物基尼龙导热复合材料具有重要的参考价值.     

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.