双马来酰亚胺在改进硅橡胶热稳定性中的作用

 双马来酰亚胺能改进硅橡胶在空气或氧气中的热稳定性。热老化试验和热降解动力学分析表明,其机理可能是双马来酰亚胺能优先与氧作用,避免了硅橡胶链上侧甲基被氧化,减轻了交联密度的提高,从而提高了硅橡胶的热稳定性。     

硅橡胶包覆十八烷/聚(St-MMA)储能微胶囊复合材料制备及热性能

以十八烷/聚(苯乙烯-甲基丙烯酸甲酯)(P(St-MMA))微胶囊为相变材料,硅橡胶作为载体,制备了十八烷/P(St-MMA)/硅橡胶复合材料。研究了微胶囊的加入方式及加入量,硅橡胶包覆方法。通过红外光谱(IR)和扫描电镜(SEM)研究复合材料的结构和形貌。通过力学性能测试如拉伸强度、扯断伸长率,确定最佳的加工方法。通过热重分析法(TG)、差示扫描量热法(DSC)和储热性能对复合材料的热性能进行研究。结果表明,十八烷制成微胶囊加入到硅橡胶中,且微胶囊加入量是2份时,十八烷/P(St-MMA)微胶囊/硅橡胶的热稳定性热稳定性及力学性能较好。室温硅橡胶包覆微胶囊掺混固化法制备的复合材料的力学性能优于直接共混后热固化法和混炼涂抹后热固化法。十八烷/P(MMA-St)/硅橡胶复合材料的焓值为67.6J/g,储能效果好。     

耐高温高导热硅橡胶的研究与应用进展

概述了导热硅橡胶的种类、组成、固化机理和应用及发展方向。分析了硅橡胶的热老化机理,概述了几种提高硅橡胶耐热老化性能的方法,指出添加含杂原子聚硅氧烷是提高硅橡胶耐热性和综合性能的一条非常重要的有效途径。同时系统阐述了导热硅橡胶的导热理论和机理及提高硅橡胶导热性的方法,概述了导热填料的种类、晶体结构、粒径及制法、取向和纤维化及表面处理和复合杂化对硅橡胶导热性能的影响。     

真空紫外辐照对加成型硅橡胶光学性能的影响

考察了加成型硅橡胶在真空环境中经1000ESH紫外辐照后的性能变化。结果表明,辐照后材料均出现发黄的现象,光学透过率大幅度 下降,同时加入硅酸钾包覆后制备的热控涂层反射率下降。经原位测试与离位测试,发现加成型硅橡胶在两种不同条件下测得的结果差异较小,而在有机硅橡胶中加入ZnO后原位与离位测试结果则差异明显,表现出明显的漂白作用。     

可膨胀石墨对室温硫化硅橡胶性能的影响

以α,ω-二羟基聚二甲基硅氧烷为基胶、纳米碳酸钙为填料、可膨胀石墨为阻燃剂,制得室温硫化硅橡胶.采用垂直燃烧、氧指数、热分析、拉伸和扫描电镜等手段研究了硅橡胶/可膨胀石墨体系的阻燃、热分解、力学性能,以及燃烧前后的微观形态.研究结果表明,可膨胀石墨是硅橡胶的良好阻燃剂,添加剂的质量分数为10%时,硅橡胶达到UL94 V...     

双马来酰亚胺在改进硅橡胶热稳定性中的作用

双马来酰亚胺能改进硅橡胶在空气或氧气中的热稳定性。热老化试验和热降解动力学分析表明,其机理可能是双马来酰亚胺能优先与氧作用,避免了硅橡胶链上侧甲基被氧化,减轻了交联密度的提高,从而提高了硅橡胶的热稳定性。     

硅氮烷添加剂的水解稳定性对硅橡胶热稳定性的影响

采用一种新的方法研究了硅氮烷水解反应的动力学规律 ,根据实验数据测出硅氮烷水解速率对硅氮烷的浓度符合一级动力学关系 .计算出了几种硅氮化合物与水蒸气反应的表观活化能 ,结果表明硅氮烷的结构与其水解反应的表观活化能有密切的关系 .硅原子或氮原子上带有较大空间位阻的基团后 ,其水解稳定性提高 .其中六苯基环三硅氮烷 4的水解表观活化能为 2 14kJ mol,而苯基硅氮聚合物 5的水解表观活化能更达到 2 91 3kJ mol.添加到硅橡胶中的硅氮化合物水解表观活化能越大 ,即水解稳定性越高 ,其改进硅橡胶热稳定性的效果越好 .将 4和 5添加到硅橡胶生胶中 ,35 0℃下老化 2 4h的热失重分别为 0 96 %和 0 6 % .     

在线热裂解-气质联用分析缩合型和加成型硅橡胶

用在线热裂解-气质联用技术对缩合型硅橡胶和加成型硅橡胶分别进行分析,在其裂解产物中都检测到一系列的二甲基环硅氧烷环体.比较二者的裂解产物发现:缩合型硅橡胶非常容易发生裂解反应,产生低分子量的二甲基硅氧烷环体;而加成型硅橡胶相对难以裂解,有一定量的高级二甲基硅氧烷环体产生.除此之外还检测到微量的含氢环体和含乙烯基环体.这为缩合型和加成型这两种硅橡胶分析提供实验依据.     

一种提高有机硅导电橡胶复合材料导电和电磁屏蔽性能的方法

描述了一种利用多元复合导电网络提高有机硅橡胶复合材料导电和电磁屏蔽性能的思想。这种含有多元复合导电网络的复合材料是通过将镀银泡沫、导电填料和有机硅橡胶复合在一起而制备的。利用扫描电子显微镜观察了复合材料的微观结构,采用电阻测试仪、矢量网络分析仪、热失重分析仪分别研究了复合材料的导电性、电磁屏蔽性能及热稳定性,并探讨了补强剂SiO2对这些性能的影响。结果表明,2%碳纳米管/导电泡沫/硅橡胶多元复合体系相比于2%碳纳米管/硅橡胶单一复合体系电阻率降低了6个数量级,平均电磁屏蔽效能由12dB提高到52dB,增大了4倍。当导电填料换为炭黑后,2%炭黑/导电泡沫/硅橡胶多元复合体系相比于2%炭黑/硅橡胶单一复合体系电阻率降低了7个数量级,平均电磁屏蔽效能由10dB提高到50dB,增大了5倍。由于多元复合导电网络,材料的导电性能和电磁屏蔽性能大幅度提升。此外,补强剂的加入增大了复合材料的热稳定性,但降低了其导电和电磁屏蔽性能。     

钛酸钾晶须对热硫化硅橡胶性能的影响

研究了钛酸钾晶须对热硫化硅橡胶复合材料的硫化特性、力学性能及热稳定性的影响,通过扫描电镜观察了复合材料的断面及晶须在基体中的分散性。结果表明:钛酸钾晶须能促进硅橡胶的硫化,提高其最高扭矩;同时,钛酸钾晶须对硅橡胶具有一定的补强作用,拉伸强度、硬度等随晶须用量的增加而增大;钛酸钾晶须的引入,使硅橡胶复合材料的热稳定性明显提高,填充量为9vol%时,与纯硅橡胶相比,复合材料的热分解温度提高了65℃,Kissinger法求出填充量为12vol%的钛酸钾晶须/硅橡胶复合材料的热分解活化能为193.62kJ/mol,高于相同填充量的白炭黑/硅橡胶复合材料,具有较好的热稳定性。     

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.     

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.     

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.     

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.