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 % .     

硅氮化合物的结构与水解稳定性的关系

采用硅氮化合物本体与水蒸汽直接作用的方法,研究了一系列硅氮化合物的结构与水解稳定性之间的关系.结果表明,空间位阻越大则硅氮化合物水解稳定性越好,环张力对硅氮烷的水解稳定性有一定的影响,但空间位阻的作用更为显著.带有苯基的环二硅氮烷、六苯基环三硅氮烷和含硅氮键的高分子聚合物具有较大的空间位阻,因此水解稳定性非常好.     

不同结构的硅氮烷与羟基硅油的本体反应

讨论了不同结构的硅氮烷与羟基硅油的本体反应，研究了反应动力学，结果表明该本体反应为二级反应，其反应活化能约为４４ＫＪ／ｍｏｌ：硅氮烷中的氮含量愈高、Ｎ／Ｓｉ比愈大、结构中环张力的存在等都使反应速度加快、硅原子上引入苯基取代基会使反应速度减慢。同时也讨论了温度对反应速度的影响。     

硅氮烷的合成与应用研究进展

硅氮烷根据原料以及合成方法的不同可分为链硅氮烷、环硅氮烷、聚硅氮烷等. 有机硅氮化合物由于其含有的硅氮键、氮氢键的独特性质, 在陶瓷前驱体制备、耐热材料的制备、辉光放电反应、高效液相色谱等方面有了越来越重要的应用.介绍了硅氮烷的一些最新合成与应用研究进展.     

环硅氮烷的合成与应用研究进展(1)——环二硅氮烷

环二硅氮烷是有机硅氮化合物中结构与性能比较特殊的一类化合物,在材料化学及配位化学领域有重要的潜在应用前景.综述了近年来环二硅氮烷的合成方法与应用研究进展.在合成方面,主要分为3条路线,分别由环三硅氮烷锂盐、取代硅胺及六氯化二硅为起始物.在应用领域,介绍了环二硅氮烷的离子开环聚合、等离子聚合、与其它单体的共聚、水解和金属配合物的制备及其在陶瓷、粘合剂和预想的催化剂上的应用.     

疏水化SiO_2纳米颗粒及其超疏水涂层的制备

基于Stber方法,以正硅酸乙酯为硅源、乙醇为溶剂、N,N,N',N'-四甲基-1,4-丁二胺为催化剂,通过加入六甲基二硅杂氮烷作为共水解前驱体和表面改性剂,得到SiO_2溶胶具有良好的疏水性能.实验结果表明,六甲基二硅杂氮烷将甲基引入溶胶体系,使溶胶不需要经过额外的全氟硅烷疏水化处理,直接得到疏水性能SiO_2溶胶.论文还详细研究了催化剂和六甲基二硅杂氮烷对溶胶疏水性能的影响,并对其作用机理进行了讨论.     

杂氮硅三环侧链上基团转换反应的研究

我们曾报道了从氯烷基杂氮硅三环通过硫氰化,烷氧化反应得到相应的硫氰烷基和烷氧基杂氮硅三环,并研究了在各种反应条件下杂氮硅三环本身的稳定性。     

超支化聚碳硅氮烷的合成与表征

聚碳硅氮烷是一种新型含硅有机金属聚合物,其主链由硅氮碳连接而成,侧链为有机基团;与其它含硅聚合物(聚硅氮烷、聚碳硅烷等)类似,聚碳硅氮烷适于用做力学性能极佳且耐高温氧化的氮化硅(Si3N4)和氮化硅/碳化硅(Si3N4/SiC)复相陶瓷的前驱体.[1]超支化聚合物具有溶解性好、粘度低     

氨硼烷催化水解制氢

氢气作为全球公认的清洁能源载体,备受关注。寻找安全高效的储氢材料以转型到氢能社会是当前氢能应用面临最大的挑战之一。氨硼烷(NH₃BH₃,AB)具有非常高的储氢质量分数(19.6 wt%)和体积储氢密度(0.145 kgH₂/L),因其在储氢和放氢性能方面的显著优势,被认为是一种颇具应用潜力的化学储氢材料。氨硼烷能够通过热解、醇解和水解放出氢气。其中,氨硼烷水解制氢可以通过催化剂进行可控放氢,且具有反应条件温和、不产生CO(易使催化剂中毒)等优点,被认为是一种安全高效和实用性强的制氢技术。本文简要介绍了氨硼烷的性质和合成,阐述了氨硼烷水解制氢的机理,综述了近年来氨硼烷水解制氢催化剂的研究进展,分析了碱对氨硼烷水解制氢的促进作用,并讨论了水解产物回收利用问题。     

聚硼硅氮烷陶瓷前驱体分子结构设计和合成*

聚硼硅氮烷是制备高性能硅硼 碳氮（SiBCN）复相陶瓷的主要聚合物前驱体,在耐高温、抗氧化高性能陶瓷领域中具有重要的研究价值。本文分4个方面,即基于硼吖嗪的聚硼硅氮烷、侧基含有环硼氮烷或单硼烷的聚硼硅氮烷、基于多官能硼烷构筑的聚硅氮烷和含硼聚硅基碳化二亚胺,从聚硼硅氮烷分子结构设计、改性、合成及在多维尺寸材料中初步应用的角度综述了该领域国内外研究的新进展,指出了聚硼硅氮烷陶瓷前驱体设计合成研究发展中值得关注的新方向。     

Dimerisation of a silicenium ylid by methanide and silylamine migration

The thermal elimination of LiF from lithium aminofluorosilanes provides a simple synthetic route to four-membered silicon-nitrogen rings. In attempts to inhibit sterically the otherwise ready dimerisation of such lithium salts, t-butyl, mesityl and silylamine substituents were introduced. The lithiation of the fluorotris(silylamino)silane (Me₃SiNMe)₂SiF-NHSiMe₂CMe₃ and the thermal elimination of LiF led to the formation of a cyclodisilazane, involving migration of a methanide and a silylmethylamine in one of the monomer precursors. The crystal structure of this product has been determined from 3375 unique diffractometer-measured intensities, and refined to R = 0.070. The space group is P2₁/_n, with a 12.458(2), b 22.589(3), c 16.376(4) Å, β 102.33(1)° and Z = 4.     

STRUCTURE OF 1,3-BIS(DIPHENYLHYDROXYSILYL)-2,2-DIMETHYL-4,4-DIPHENYL-CYCLODISILAZANE

<正> M =667.0, monoclinic, P21/n, a=11.854(2), b=10.136(1), c=29.931(4) A, β=93.51(1)°, Z=4, V=3588.9(8)A3, Dx=1.23 Mgm-3, λ(MoKα)=0.71069A, μ(Mo-Kα)=2.0, F(000)=1408, room temperature, R=0.072 for 3015 reflections. The structure was solved by direct method.The cyclodisilazane ring is a flattened tetrahedron. The three bonds on N(1) and N(2), respectively, are in a plane. The mean bond lengths of Si-C (methyl), Si-C(phenyl), Si-O, Si-N(endocyclic) and Si-N(exo-) are 1.839, 1.847, 1.636, 1.744 and 1.711A, respectively.     

氨化大孔球状聚氯乙烯固定化木瓜蛋白酶的研究

以氨化大孔球状聚氯乙烯为载体,采用戊二醛载体交联的方法,将木瓜蛋白酶进行了固定化。以酪蛋白为底物,测定了固定化酶的活力回收。研究了固定化条件对固定化酶活力回收的影响。同时,对所得固定化酶的性质,如温度-活力关系、pH-活力关系、热稳定性以及重复使用性进行了考察。结果表明,所得固定化木瓜蛋白酶具有较好的稳定性和重复使用性。     

硅氮化合物在改进聚硅氧烷热稳定性中的作用

本文研究了聚硅氧烷在硅氮化合物或二苯基二羟基硅烷、水以及它们同时存在下的热稳定性。硅氮化合物能使聚硅氧烷在350℃的热稳定性大大提高;而二苯基二羟基硅烷和水能促进硅氧烷主链的降介,但同时有硅氮化合物存在,这种促进作用将会消失。所以硅氮化合物能阻止由硅羟基和水引起的降介。同时也是获得耐350℃聚硅氧烷的简便方法。     

Quantum-Chemical Study of the Adducts of Silicon Halides with Nitrogen-containing Donors: II.1 Calculation of a Donor-Acceptor Bond Energy. Complex trans-SiH4·2NH3

Structural and thermodynamic characteristics of the trans-SiH₄·2NH₃ adduct were obtained by ab initio and DFT (RHF and B3LYP) calculations. Scanning the potential energy surface (PES) of the com plex showed that its structure corresponds to a local minimum, whereas the global minimum corresponds to the free fragments. The energy of the silicon-nitrogen chemical bond was calculated with inclusion of fragment rearrangement energies and basis set superposition error. The procedure offered for calculating the Si-N bond energy was extended to adducts of silicon halides with ammonia. It was found that the energy of SiX₄ rearrangement contributes most to the energies of donor-acceptor bonds in mono- and diammoniates of silicon tetrahalides.     

Polyisobutylene‐based polyurethanes. VI. Unprecedented combination of mechanical properties and oxidative/hydrolytic stability by H‐bond acceptor chain extenders

We describe the design, synthesis, characterization, and testing of novel polyurethanes (PUs) exhibiting unprecedented combinations of outstanding mechanical properties and oxidative/hydrolytic stabilities. This achievement is due to the use of polyisobutylene (PIB) soft segments plus flexible H‐bond acceptor chain extenders (HACEs): the PIB imparts superior oxidative/hydrolytic stability and the HACE produces reinforcing H‐bonds, which lead to outstanding mechanicals. Oxidative/hydrolytic stability was quantitated by retention of tensile strength and elongation after exposure to nitric acid. PUs containing 60–70% PIB retain their mechanical properties, whereas Carbothane®, Bionate®, and Elast‐Eon?, PUs marketed for chemical stability, degrade severely under the same conditions. Various HACEs were identified (e.g., hexaethylene glycol, tripropylene glycol, tributylene glycol, 3,3′‐diamino‐N‐methyl‐dipropylamine, etc.) and their effect on mechanical properties was investigated. A PIB‐ and HACE‐containing PU exhibited 29.2 MPa tensile strength, 620% elongation, and 80 Shore A hardness. Properties were analyzed in terms of stress–strain profiles, differential scanning calorimetry traces, dynamic mechanical thermal analysis plots, and oxidative/hydrolytic stability. The properties of various PIB‐based rubbers, that is, thermoplastic PUs, SIBSTAR®, and thermoset butyl rubber are compared. The novel PUs are promising candidates for biomaterials and industrial applications where a combination of mechanical properties and oxidative/hydrolytic stability is of the essence. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2361–2371, 2010     

Hydrolytic stability of the ester bond in aminoacyl derivatives of N-acetylglucosamine, glucosamine, and N-acetylneuraminic acid

Summary The hydrolytic stability of the ester bond of O-aminoacyl derivatives of N-acetylglucosamine, glucosamine (base), and methyl N-acetylneuraminate has been studied at pH 1–8. It has been shown that the stability of the O-aminoacyl derivatives of N-acetylglucosamine is comparable with that of the corresponding glucose derivatives. The presence of a free amino group in glucosamine leads to a considerable labilization of the ester bond. The ester bond of the O-aminoacyl derivatives of methyl N-acetylneuraminate is characterized by a very high lability, and this must be taken into account in working with biopolymers.Khimiya Prirodnykh Soedinenii, Vol. 4, No. 1, pp. 28–32, 1968     

Stabilisation of the transition state of phosphodiester bond cleavage within linear single-stranded oligoribonucleotides

The effect of base sequence on the stability of the transition state (TS) of phosphodiester bond cleavage within linear single-stranded oligoribonucleotides has been studied in order to better understand why the reactivity of some phosphodiester bonds is enhanced compared to an unconstrained linkage. Molecular dynamics simulations of 3.0 ns were carried out for 14 oligonucleotides that contain in the place of the scissile phosphodiester bond a phosphorane structure mimicking the TS of the bond cleavage. The hydrolytic stability of the same oligonucleotides had previously been reported. Both the non-bridging oxyanions and the leaving 5[prime or minute]-oxygen of the pentacoordinated phosphorane moiety were observed to form hydrogen bonds with solvent water molecules in a similar way with all the compounds studied. In addition, water mediated hydrogen bonds between the phosphorane non-bridging oxyanions and the bases of the 3[prime or minute]-flanking sequence were detected with some of the compounds, but not with the most labile ones. Hence, it seems that the enhanced cleavage of some internucleosidic linkages does not result from the TS stabilisation by hydrogen bonding. With heterooligomers, the stacking of bases next to the cleavage site was observed to be enhanced on going from the initial state to the TS, whereas within uracil homooligomer, having initially negligible stacking, no change in the magnitude of stacking was seen. Accordingly, while strong stacking in the initial state is known to retard the phosphodiester bond cleavage, it may in the TS accelerate the reaction. Therefore, enhanced stacking on going from the initial state to transition state appears to be a factor that markedly contributes to the hydrolytic stability of phosphodiester bonds within oligonucleotides and may, at least partly, explain accelerated cleavage compared to fully unconstrained bonds, such as those in polyuridylic acid.