硅倍半氧烷改性聚酰亚胺(PI/Si)复合膜性能

通过在聚酰亚胺(PI)中分别添加笼型八氨基苯基硅倍半氧烷(OAPS)、 笼型八苯基硅倍半氧烷(OPS)、 梯形聚苯基硅倍半氧烷(PPSQ)和无机纳米SiO₂, 制备了4种含硅聚酰亚胺(PI/Si)复合膜. 对PI/Si复合膜的相容性、 力学性能、 热性能和阻燃性能进行了研究. 结果表明, OAPS与PI间展现出较好的相容性, PPSQ次之, 而OPS, SiO₂与PI的相容性较差; 但相容性与复合膜的力学和热性能无明显的对应关系. SiO₂可提高PI的力学性能; PI/OAPS复合膜的T_g最高; OAPS, PPSQ或SiO₂的加入使PI复合膜的热稳定性稍有提高, 而少量OPS的加入大大降低PI膜的热稳定性. 这类PI/Si复合膜的显著特点是能够大幅提高PI膜的极限氧指数, 含硅化合物能够增加PI燃烧后残炭量, 使残炭的形貌得到显著改善. PI/Si复合膜在燃烧过程中在表面形成一层白色含硅包裹层, 起到隔热隔氧及保护内层有机物不被燃烧的作用. 硅倍半氧烷对炭层形貌的改善显著, 展现出比SiO₂更好的阻燃性能.     

多面体低聚八氨基苯基硅倍半氧烷合成方法改进及其表征

以八硝基苯基硅倍半氧烷(ONPS)为原料, 5% Pd/C 和FeCl₃ 为催化剂, 水合肼为还原剂, 在四氢呋喃溶液中反应 1 h 合成了八氨基苯基硅倍半氧烷(OAPS). 相比文献中已有的其它合成方法, 该方法合成过程简单且稳定, 催化效率高、产率高、周期短. 通过FTIR, ¹H NMR, GPC 对产物进行了表征, 证明了硝基已完全转化. 通过催化剂的控制, 分离出ONPS 向OAPS 转化过程中的一种含有羟胺和二羟胺基团的中间体. 分析了OAPS 合成机理, 提出了ONPS 和水合肼的反应历程. 认为ONPS 中的硝基先经过2 电子转移转化为二羟胺化合物, 然后经过脱水加氢生成羟胺化合物, 最后再经过脱水加氢生成OAPS; 在有ONPS 存在的情况下, 水合肼主要转化为氮气和氢气, 待ONPS 完全转化为OAPS 后, 水合肼转化为氮气和氨气.     

多面体低聚八(二苯砜基)硅倍半氧烷合成优化及磺酰化机理研究

以笼型低聚八苯基硅倍半氧烷(OPS)为原料,AlCl3为催化剂,苯磺酰氯为磺酰化试剂,在二氯甲烷溶液中反应72h,合成了笼型八(二苯砜基)硅倍半氧烷(ODPSS).该方法合成过程简单稳定,产率高.通过FTIR、MALDI-TOF MS、1H NMR、13C NMR、29Si NMR和元素分析对产物进行了表征,证明OPS已完全转化为ODPSS.通过改变溶剂、催化剂、反应时间和各反应物物质的量之比,优化了反应条件,分析了反应机理,建立了该体系下OPS的磺酰化反应机理模型.     

多面齐聚硅倍半氧烷研究进展

总结了多面齐聚硅倍半氧烷的研究进展,主要介绍了它的合成方法、合成机理和应用,着重介绍了它在二氧化硅模型、树枝状大分子、多孔材料以及聚合物纳米杂化材料中的应用。     

多面体低聚八硝基苯基硅倍半氧烷纯度分析

使用高效液相色谱-电喷雾四级杆飞行时间质谱(HPLC-ESI-Q-TOF MS)联用技术对八硝基苯基硅倍半氧烷(ONPS)纯度进行分析, 从而判定ONPS产物峰及杂质峰的位置, 根据ONPS峰和杂质峰的面积比计算ONPS的纯度. 通过改变HPLC的洗脱梯度和测试时间, 将ONPS产物中的杂质峰完全分开, 测得硝基苯基硅倍半氧烷(NPS)质量分数为97.55%, 其中ONPS的纯度约为92.42%, 产物中含有九硝基八苯基硅倍半氧烷(9-NPS)约5.13%, 其它杂质含量约为2.45%. 通过对ONPS高效液相色谱图峰形和同分异构体极性情况分析, 进一步证明ONPS分子中硝基取代发生于对位和间位. 使用超高效液相色谱(UPLC)对ONPS进行分析, 以更高的分离效率验证了HPLC的结果. 该方法可作为ONPS纯度的分析方法.     

主链含酰亚胺环和炔基的聚酰亚胺型聚氨酯弹性体的合成及阻燃性能简

以均苯四甲酸酐、D,L-苯丙氨酸和1,4-丁炔二醇为原料合成了一种含有酰亚胺环和炔基的二醇,并以其为扩链剂,采用预聚体法,与4,4-二苯基甲烷二异氰酸酯(MDI)和聚四氢呋喃醚二醇(PTMG)反应,合成了不同硬段含量的主链含有酰亚胺环和炔基的热塑性聚酰亚胺型聚氨酯弹性体. 用红外光谱(FTIR)、电子拉力机、热失重分析(TG)、广角X射线衍射(XRD)、UL-94垂直燃烧和极限氧指数对聚酰亚胺型聚氨酯弹性体进行了表征. 结果表明,这种聚氨酯呈现出无定形结构;其拉伸强度随着硬段含量的增加而增大;与传统的热塑性聚氨酯相比,酰亚胺环和炔基改性的聚酰亚胺型聚氨酯弹性体的热分解过程非常缓慢,呈现出较好的热稳定性;不同硬段含量的聚酰亚胺型聚氨酯弹性体的UL-94垂直燃烧均达到V-2级别;其极限氧指数随着硬段含量的增加而增大.     

苯基笼状倍半硅氧烷(TSP-POSS)改性聚氨酯的分子模拟和热性能研究

采用分子力学及分子动力学方法,构建了质量百分比分别为0 wt%、3.06 wt%、6.56 wt%、10.13wt%、12.11 wt%、15.36 wt%和19.87 wt%共7种TSP-POSS杂化聚氨酯的分子结构模型,通过对均方位移、径向分布函数、XRD衍射图谱的分析,在分子水平上研究了半笼型TSP-POSS的引入对聚氨酯分子链结构及热性能的影响.结果表明,当TSP-POSS含量低于12.11 wt%时,随着TSP-POSS质量分数的增加,分子链之间的平均距离增大,分子间相互作用减小,聚合物分子链的运动性增强;当TSP-POSS含量高于12.11 wt%时,TSP-POSS自身会团聚成晶簇,降低了聚合物分子链的运动能力并由无定形聚集状态转变为层状半结晶结构.通过对7种体系的体积-温度函数分析,证明TSP-POSS的引入在一定程度上能显著提高聚氨酯杂化材料的玻璃化转变温度,在一定程度上增强其热稳定性.     

纳米尺度超声显影微囊的制备及性能表征简

采用双乳液-溶剂挥发法制备了内部包封氟碳液体的聚乳酸-甲氧基聚乙二醇两嵌段共聚物(MePEG-b-PLA)基超声显影纳米微囊;用2种不同嵌段比的MePEG-b-PLA共聚物研究共聚物组成与纳米囊性能的关系;选用聚乙烯醇(PVA)、羧甲基葡聚糖(CMG)和壳聚糖(CS) 3种乳化剂对纳米囊表面进行亲水性修饰. 对所制备纳米囊的粒径、Zeta电位、形貌和水溶液稳定性进行了表征. 结果表明,利用质量分数为1%的PVA和质量分数为1%的CMG组成的复配乳化剂和m(MePEG)：m(PLA)= 1：3的聚合物制得的纳米囊的平均粒径为432.9 nm,水溶液稳定性优良. 利用超声仪对纳米囊体外超声显影性能进行研究,结果表明,所得聚乳酸-甲氧基聚乙二醇纳米囊具有更好的中心成像区域灰度值和更持久的体外超声显影效果. 结合3-(4,5-二甲基噻唑-2)-2,5-二苯基四氮唑溴盐(MTT)比色法研究证实该纳米囊具有低细胞毒性. 在超声影像学领域具有良好的应用前景.     

水下超疏油聚(3,4-乙烯基二氧)噻吩薄膜的制备简

以离子液体溴化(1-己基-3-甲基咪唑盐)作为电解质和掺杂剂采用电化学一步法制备了微纳米复合结构的聚(3,4-乙烯基二氧噻吩)薄膜,薄膜由槽内排布着纳米珠链的棒状结构组成. 研究表明,通过控制电流密度的大小,可以调节棒状结构和珠状结构的平均直径. 离子液体中的咪唑阳离子和对阴离子均掺杂到聚合物中,该薄膜具有可逆的电化学活性及水下超疏油特性.     

倍半硅氧烷改性环氧树脂的研究进展

倍半硅氧烷是近年发展起来的一种分子水平的有机无机杂化材料。文章介绍了倍半硅氧烷的结构、合成以及笼型倍半硅氧烷（POSS）基高分子复合材料的结构及合成方法。倍半硅氧烷改性聚合物可以提高聚合物的热性能、阻燃性能和物理机械性能等。文章综述了倍半硅氧烷改性环氧树脂的研究进展。     

Polyurethane Networks Nanoreinforced by Polyhedral Oligomeric Silsesquioxane

Summary: Octaaminophenyl polyhedral oligomeric silsesquioxane (OapPOSS) was used as a crosslinking agent together with 4,4^′‐methylenebis‐(2‐chloroaniline) to prepare polyurethane networks containing POSS. Fourier transform infrared spectroscopy (FT‐IR), dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA) were employed to characterize the POSS‐reinforced polyurethane. The POSS‐containing PU networks displayed enhanced glass transition temperatures (T_gs) and the storage moduli of the networks of the glassy state and rubber plateaus were also observed to be significantly higher than that of the control polyurethane although only a small amount of POSS was incorporated into the systems. The results can be ascribed to the significant nanoscale reinforcement effect of POSS cages on the polyurethane matrix. TGA results showed the thermal stability was also improved with incorporation of POSS into the system.

Dynamic mechanical spectra of PU and PU nanocomposites containing POSS.     

含多面低聚倍半硅氧烷新型杂化聚合物的合成

基于多面低聚倍半硅氧烷（POSS）的杂化聚合物是近年发展起来的一类新型有机/无机杂化材料,性能独特,应用前景广阔。本文综述了含POSS新型杂化聚合物的合成研究进展,涉及自由基溶液聚合、可控活性聚合、开环易位聚合、缩聚和配位聚合。     

Enhancement of Electrochromic Contrast by Tethering Conjugated Polymer Chains onto Polyhedral Oligomeric Silsesquioxane Nanocages

Copolymerization of aniline with octa(aminophenyl) silsesquioxane (OAPS) was performed, which resulted in polyaniline‐tethered, polyhedral oligomeric silsesquioxane (POSS‐PANI), with star‐like molecular geometry. The spectro‐electrochemical studies show that the electrochromic contrast of POSS‐PANI is much higher than that of polyaniline (PANI). The great improvement can be attributed to the more accessible doping sites and the facile ion movement during the redox switching, brought by the loose packing of the PANI chains. This was evidenced by a drastic increase in ionic conductivity, a decrease in the electrical conductivity, and a decrease in the crystallinity and crystal size, with the increase of the OAPS concentration in the POSS‐PANI.

     

Poly(4‐vinylpyridine) Nanocrosslinked by Polyhedral Oligomeric Silsesquioxane

Summary: Octa(propylglycidyl ether) polyhedral oligomeric silsesquioxane (OpePOSS) was used as the crosslinking agent to prepare the nanocrosslinked poly(4‐vinylpyridine) (P4VP) with POSS content up to 55.2 wt.‐%. The formation of the crosslinked structure is ascribed to the macromolecular reaction between pyridine rings of P4VP and epoxide groups of OpePOSS. The POSS‐crosslinked P4VP displayed enhanced glass transition temperatures (T_gs) and an improved thermal stability in terms of the results of thermal analysis.

Crosslinking of poly(4‐vinylpyridine) with octa(propylglycidyl ether) polyhedral oligomeric silsesquioxane.     

Positive Luminescent Sensor for Aerobic Conditions Based on Polyhedral Oligomeric Silsesquioxane Networks

There are numerous numbers of hypoxia-selective luminescent probes based on oxygen quenching of phosphorescence.We show a unique design for luminescent probes to detect hyperoxia utilizing hybrid networks consisting of aggregation-induced emission(AIE)-active dyes and disulfide linkers.At the initial state,emission from the AIE-active dyes is inducible by suppressing energy-consumable intramolecular motions in the hybrid matrices,while the decrease in intensity was detected by releasing molecular motions corresponded to bond scission at the disulfide linkers.Particularly,it was shown that this process selectively proceeds in hypoxia.As a result,positive luminescent signals were obtained in hyperoxia.     

含POSS侧基的非环二烯烃易位聚合及离子型杂化聚合物表征

基于七异丁基-胺丙基-多面体低聚倍半硅氧烷(POSS-NH₂)与溴丁烯或溴代十一烯反应, 一步法合成了含POSS侧基的两种杂化二烯烃. 以钌卡宾络合物为催化剂的非环二烯烃易位(ADMET)聚合, 短链二烯烃未能发生, 而长链二烯烃能顺利实现. 将杂化二烯烃转变为离子型杂化二烯烃, 其ADMET聚合活性较高, 随着反应时间延长, 聚合物分子量明显增大, 分子量分布变窄, 体现了逐步聚合的特征. 核磁共振分析揭示了聚合物的不饱和结构和聚合反应的变化过程. 主链不饱和的无定形聚合物, 经氢化作用转变为饱和的离子型杂化聚乙烯, POSS基团精确地连接在聚乙烯骨架的侧位上, 且POSS基团和聚乙烯骨架均表现出较强的结晶能力. 这种离子型杂化聚乙烯具有球形的单分子或聚集形态, 可直接构筑纳米尺度的聚合物材料.     

Use of Polyhedral Oligomeric Silsesquioxane (POSS) in Drug Delivery,Photodynamic Therapy and Bioimaging

Polyhedral oligomeric silsesquioxanes (POSS) have attracted considerable attention in the design of novel organic-inorganic hybrid materials with high performance capabilities. Features such as their well-defined nanoscale structure, chemical tunability, and biocompatibility make POSS an ideal building block to fabricate hybrid materials for biomedical applications. This review highlights recent advances in the application of POSS-based hybrid materials, with particular emphasis on drug delivery, photodynamic therapy and bioimaging. The design and synthesis of POSS-based materials is described, along with the current methods for controlling their chemical functionalization for biomedical applications. We summarize the advantages of using POSS for several drug delivery applications. We also describe the current progress on using POSS-based materials to improve photodynamic therapies. The use of POSS for delivery of contrast agents or as a passivating agent for nanoprobes is also summarized. We envision that POSS-based hybrid materials have great potential for a variety of biomedical applications including drug delivery, photodynamic therapy and bioimaging.