硅倍半氧烷-环氧杂化材料的研究

将环己基硅倍半氧烷硅三醇与环氧树脂E-51在环烷酸钴催化下进行反应,制成硅倍半氧烷-环氧杂化材料.通过傅立叶红外光谱、差热分析证实,反应具有较低的活化能,只是笼型结构外围的Si-OH与环氧基团进行反应,反应对笼型结构无影响;动态力学性能与热稳定性的分析表明,与4,4′-二氨基二苯砜固化的环氧固化物相比,硅倍半氧烷-环氧杂化材料具有较高的玻璃化转变温度、储能模量及热分解温度和热残余量.     

有机-无机杂化纳米结构体——多面体低聚硅倍半氧烷研究进展

多面体低聚硅倍半氧烷是基于化学键合作用形成的分子内杂化体系,其改性后的材料是一类具有广泛潜在应用价值的新型有机-无机杂化材料。介绍了多面体低聚硅倍半氧烷单体的结构、性能、单体及其衍生物的合成,以及其改性聚合物材料在航空、航天、生物、电子等高科技领域内的应用前景。针对国内的研究现状,指出低聚硅倍半氧烷-聚合物杂化体系研究所存在的问题。     

笼形八苯基硅倍半氧烷的合成及表征

在控制水的滴加速度和体系温度的前提下,苯基三氯硅烷首先发生水解缩合形成苯基硅氧烷预聚体,然后在微量KOH催化剂作用下,制得八苯基硅倍半氧烷,收率大于90%。用傅立叶红外光谱、29Si核磁共振光谱、质谱、元素分析和热分析等手段,对它的结构和性质进行了表征。该物质的初始分解温度(失重5%)为436.8℃,热稳定性高。目前正在进行放大实验。     

聚(乙烯基)硅倍半氧烷的结构表征

以乙烯基三乙氧基硅烷为原料,通过控制水解聚合条件制得聚(乙烯基)硅倍半氧烷。IR光谱表征产物中形成了Si—O—Si的骨架结构,29SiNMR表征说明产物是以笼形结构为主,用GPC测得的摩尔质量接近五面体(T6)和六面体(T8)结构的笼形聚(乙烯基)硅倍半氧烷;通过对产物平均几何参数的计算,确定产物为笼形T6结构的聚(乙烯基)硅倍半氧烷。     

多面体低聚硅倍半氧烷的研究进展

综述了多面体低聚硅倍半氧烷（POSS）的结构特性和合成方法，重点介绍了同取代基、单官能度、双官能度、多官能度四类POSS的合成方法，比较了各种合成方法的优劣，展望了POKS合成研究的发展方向。     

EP/环氧基苯基多面体低聚硅倍半氧烷复合物的制备及其性能

通过水解缩合反应合成了环氧基苯基多面体低聚硅倍半氧烷(cy-ep-Ph-POSS),并制备了环氧树脂(EP)/cy-ep-Ph-POSS复合物,研究了复合物的热性能、力学性能以及阻燃性能.结果表明:cy-ep-Ph-POSS主要由含有6,8,10个硅原子的多面体低聚硅倍半氧烷结构组成;与纯EP相比,EP/cy-ep-P...     

笼型八苯基硅倍半氧烷对阻燃三元乙丙橡胶性能的影响

北京理工大学的高钧驰等人发现，与仅采用聚磷酸铵和季戊四醇膨胀阻燃体系的三元乙丙橡胶（EPDM）相比，同时加入20份笼形八苯基硅倍半氧烷的阻燃EPDM的阻燃性能和力学性能均有提高。极限氧指数由20．6％提高到24．2％，热释放速度峰值由576．7kW／m^2降到331．2kW／m^2，拉伸强度由0．9MPa提高到2．5MPa，扯断伸长率由303％提高到537％，     

笼形八聚(乙烯基)硅倍半氧烷的合成

以乙烯基三甲氧基硅烷为反应单体、甲醇为溶剂、四甲基氢氧化铵为催化剂,合成了正立方体的笼形八聚(乙烯基)硅倍半氧烷[(CH2CHSi O1.5)8]。讨论了反应温度、时间、碱的用量和乙烯基三甲氧基硅烷的浓度对成笼反应的影响。结果表明,较佳的工艺条件为:乙烯基三甲氧基硅烷与四甲基氢氧化铵的量之比为1∶3,乙烯基三甲氧基硅烷的浓度为0.0747g/mL,于室温下反应24h后再60℃下反应48h;此时产物的收率可达80%。产物分别用元素分析、FT-IR、1H NMR、13C NMR、29Si NMR进行了表征。     

低聚硅倍半氧烷在HTPB复合推进剂中的多功能作用

为提升复合固体推进剂的综合性能,将不同质量分数的八苯基硅倍半氧烷(OPS)、八氨基苯基硅倍半氧烷(OAPS)、八硝基苯基硅倍半氧烷(ONPS)和八(二硝基苯基)硅倍半氧烷(ODNPS)等4种有机-无机杂化结构的多面体低聚硅倍半氧烷(POSS)加入端羟基聚丁二烯(HTPB)推进剂中。使用电子万能试验机、热机械分析仪测定推进剂的拉伸力学性能;使用氧弹量热仪测定推进剂在3MPa氮气下的爆热;利用线扫描摄像燃速测定系统测定了推进剂的燃速—压强关系;采用扫描电镜、激光粒度仪和X射线衍射仪(XRD)对推进剂爆热测试后的凝聚相燃烧产物进行微观形貌、粒度及物相分析;采用同步热分析仪、扫描电镜(SEM)、透射电镜(TEM)、X射线光电子能谱仪(XPS)等对POSS影响推进剂燃烧的机理进行了分析。结果表明,4种POSS均可增强推进剂的拉伸力学性能,八氨基苯基硅倍半氧烷(OAPS)效果最优;4种POSS均可提高推进剂的燃速,ONPS质量分数为3%时,推进剂燃速及爆热最高;4种POSS均可促进推进剂铝燃烧,明显减小凝聚相燃烧产物的粒径,ODNPS效果最优。分析认为,ONPS和ODNPS热解、燃烧产生的纳米尺寸...     

笼形八乙烯基聚硅倍半氧烷的制备和表征

比较了制备八乙烯基聚硅倍半氧烷的三种酸性水解工艺。结果发现，两步水解法无论是从环保、节能和产率方面考虑，还是从产品提纯上考虑都是较理想的方法。通过IR、^29Si NMR、^1H NMR、飞行质谱及元素分析法判断，所制备的产物为八乙烯基硅倍半氧烷，与文献报道数据相吻合。产物为六面体晶体，晶胞参数为a=b=1．63nm，c=1．72nm。产物在质量损失率为5％时的温度为265．4℃，在650℃时的残余质量分数为2．8％。     

笼型单乙烯基倍半硅氧烷的合成及表征

用环戊基三氯硅烷合成不完全缩合三羟基硅氧烷［(C₅H₉)₇Si₇O₉(OH)₃］,再以乙烯基三氯硅烷和不完全缩合三羟基硅氧烷为原料,以四氢呋喃和三乙胺为混合溶剂,通过“顶角-戴帽”反应合成了笼型单乙烯基倍半硅氧烷,即1,3,5,7,9,11,13-七环戊基-15-乙烯基笼型倍半硅氧烷(VinylPOSS)。利用FTIR、¹H NMR、²⁹Si NMR、¹³C NMR、元素分析、WAXD和TGA表征了VinylPOSS的结构及热稳定性。研究结果表明VinylPOSS的产率随着反应时间的增加而提高,当反应时间为10 h时,产率高达90%;其在弱极性溶剂中具有较好的溶解性,5%失重温度为283℃,800℃残留率为56%,具有较高的热稳定性。研究了VinylPOSS和高含氢硅油(HHSF)的反应性,结果表明VinylPOSS能与含氢硅油发生α、β加成反应, 且以β加成为主。     

Preparation and characterization of nanocomposites based on polylactides tethered with polyhedral oligomeric silsesquioxane

A series of polylactides tethered with polyhedral oligomeric silsesquioxane (POSS–PLAs) were synthesized via the ring‐opening polymerization of L ‐lactide with 3‐hydroxypropylheptaisobutyl polyhedral oligomeric silsesquioxane (3‐hydroxypropylheptaisobutyl POSS) at a concentration of 0.02–2.00 mol % in the presence of a stannous(II) octoate catalyst. 1 H‐NMR spectra and a composition analysis of the POSS–PLA hybrids confirmed that 3‐hydroxypropylheptaisobutyl POSS served as an initiator for L ‐lactide in the ring‐opening polymerization. X‐ray diffraction patterns evidenced that polyhedral oligomeric silsesquioxane (POSS) molecules of POSS–PLA hybrids were well dispersed without the formation of their crystalline aggregates. The POSS–PLA hybrid with 0.50 mol % POSS content was solution‐blended with a neat polylactide (PLA) homopolymer to obtain PLA/POSS–PLA nanocomposites with various POSS–PLA contents of 1–30 wt %. The X‐ray diffraction results of the PLA/POSS–PLA nanocomposites demonstrated that the POSS–PLA was well dispersed in the neat PLA matrix. The thermal and thermooxidative degradation properties of the nanocomposites were found to be improved at POSS–PLA contents of 1–20 wt %, compared to the neat PLA. The crystallization rates and crystallinities of the PLA/POSS–PLA nanocomposites were faster and higher, respectively, with increasing POSS–PLA content because of the nucleation effect of the POSS molecules in the neat PLA matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

八乙烯基多面体低聚倍半硅氧烷的合成与表征

采用水解缩合法,在浓HCl为催化剂的条件下,以乙烯基三甲氧基硅烷为原料合成了八乙烯基多面体低聚倍半硅氧烷,并对合成产物进行了表征;研究了反应温度、反应物的投料比对产物收率的影响.结果表明,在25 ℃,反应物水解缩合21 d,乙烯基三甲氧硅烷、HCl、CH3OH三者的体积比为9∶ 12∶ 200,乙烯基三甲氧基硅烷、HCl的体积分数分别为3.90%、5.43%时,产物的收率达到最高,为26.3%.     

Synthesis and characterization of polyimide/polyhedral oligomeric silsesquioxane nanocomposites containing quinolyl moiety

A series of functional polyhedral oligomeric silsesquioxane (POSS)/polyimide (PI) nanocomposites were prepared using a two‐step approach. First, octa(aminophenyl)silsesquioxane (OAPS) was mixed with poly(amic acid) (PAA) prepared by reacting bis(4‐amino‐3,5‐dimethylphenyl)‐3‐quinolylmethane and 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride. Second, the resulting solution was subjected to thermal imidization. The well‐defined ‘hard particles’ (POSS) and the strong covalent bonds in the amide linkage between the carbon atom of the carboxyl side group in PAA and the nitrogen atom of the amino group in POSS lead to a significant improvement in the thermal and mechanical properties. Homogeneous dispersion of POSS cages in the PI is evident from scanning electron microscopy, which further confirms that the POSS molecule becomes an integral part of the organic‐inorganic inter‐crosslinked network system. Differential scanning calorimetry and dynamic mechanical analysis show that the glass transition temperatures of the POSS‐containing nanocomposites are higher than that of the corresponding neat PI system, owing to the significant increase of the crosslinking density in the PI/POSS nanocomposites. Increasing the concentration of OAPS in the PI networks decreases the dielectric constant. Pure PI and PI/POSS systems have good antimicrobial activity. Copyright © 2011 Society of Chemical Industry     

Synthesis and characterization of polybenzoxazine networks nanocomposites containing multifunctional polyhedral oligomeric silsesquioxane (POSS)

A new class of polybenzoxazine/POSS nanocomposites with network structure is prepared by reacting multifunctional benzoxazine POSS (MBZ-POSS) with benzoxazine monomers (Pa and Ba) at various compositional ratios. Octafunctional cubic silsesquioxane (MBZ-POSS) is used as a curing agent, which is synthesized from eight organic benzoxazine tethers through hydrosilylation of vinyl-terminated benzoxazine monomer (VP-a) with octakis(dimethylsiloxy)silsesquioxane () using a platinum complex catalyst (Pt-dvs). Incorporation of the silsesquioxane core into polybenzoxazine matrix could significantly hinder the mobility of polymer chains and enhance the thermal stability of these hybrid materials. For these nanocomposites, increasing the POSS content in the hybrids is expected to improve its thermal properties with respect to the neat polybenzoxazine. The morphology feature is useful to explain the thermal property changes (T_g and T_d) and AFM images show that the presence of POSS aggregation in larger scales occurs at higher POSS contents. The reason of the heterogeneous phase separation may be from the less compatibility of the inorganic silsesquioxane core with organic benzoxazine species and the homopolymerization of MBZ-POSS. In the course of the formation of the polybenzoxazine/POSS hybrids, POSS particles were separated from the polybenzoxazine rich region, leading to POSS rich domains in the range of 50-1000 nm.     

含活性氢基的八聚笼型倍半硅氧烷的合成与表征

笼形倍半硅氧烷具有较低的介电常数。采用正硅酸乙酯和季铵碱为原材料,合成了八聚四甲基铵基笼型倍半硅氧烷,并采用二甲基氯硅烷对其进行烷基取代,得到了含活性氢基的八聚笼型倍半硅氧烷。采用核磁共振29Si、13C、1H谱和凝胶渗透色谱GPC对其结构进行了表征和确认。     

笼型倍半硅氧烷改性UPR的固化性能与热性能

采用示差扫描量热仪(DSC),热重分析仪(TGA)及动态力学分析仪(DMA)研究了甲基丙烯酰氧丙基笼型倍半硅氧烷(MAP-POSS)与一缩二乙二醇型UPR、苯乙烯的等温共固化反应及动力学,测试了固化物的热性能和动态力学性能。结果表明,固化过程符合自催化反应机理,当体系中MAP-POSS质量分数为5%时,5%热失重温度和残留量5%时的温度较未加体系分别提高7℃和31℃,玻璃化转变温度降低4.2℃,热降解动力学符合1级反应。     

交联POSS-聚氨酯胶的结构与性能研究

采用含八乙烯基的POSS为原料,与不同的聚氨酯预聚体进行共聚,合成了一系列POSS基高分子胶粘剂材料。通过表面红外(ATR)、广角X射线衍射(WAXD)和动态力学分析(DMTA)等方法表征了杂化胶粘剂的热性能。     

多面齐聚倍半硅氧烷改性环氧的制备及表征

以八苯基多面齐聚倍半硅氧烷为原料通过溴代,格氏试剂与丙酮加成等反应制备了八多羟基苯基多面齐聚倍半硅氧烷,并对产物进行了FTIR表征。采用该产物改性环氧树脂,并通过热失重分析仪、示差扫描量热仪对其固化物的热性能进行了研究。结果表明:该合成具有活性官能团的多面齐聚倍半硅氧烷的方法可行。在环氧树脂中加入八多羟基苯基多面齐聚倍半硅氧烷对其固化物热稳定性影响不大,但可以显著提高材料的玻璃化转变温度,当其质量分数为5.13%时,Tg可达183.2℃。