带功能基的笼形倍半硅氧烷合成进展

笼形倍半硅氧烷(POSS)是基于化学键合作用而形成的分子内杂化体系,这种有着规整立体结构同时具有单纳米尺度的有机无机杂化分子引起了研究人员的广泛关注,独特的纳米笼形结构也为分子水平上改进高分子的科学研究提供了可能性.本文综述了多面体倍半硅氧烷(POSS)的结构、性能与合成方法,重点介绍了巯基POSS、金属杂化POSS、...     

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.     

Effect of Polyhedral Oligomeric Silsesquioxane and Sorbitol on Properties of Isotactic Polypropylene

Isotactic polypropylene(iPP) was modified by the introduction of polyhedral oligomeric silsesquio- xanes(POSS) and 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol(DMDBS). Chemical combination of (3-mercapto)- propyl-heptaisobutyl POSS with DMDBS(POSS-DMDBS), and physical mixing of DMDBS with octaisobutyl POSS (iso-POSS/DMDBS) or trisilanolisobutyl POSS(tri-POSS/DMDBS) were applied respectively to modifying iPP, and the effects of POSS and DMDBS on crystallization, rheological and mechanical properties of iPP were systematically investigated. The results indicate that iso-POSS/DMDBS and tri-POSS/DMDBS were more effective than POSS-DMDBS on the improvement of the crystallization behavior of iPP due to the higher crystallization temperature, while the crystallinity of iPP containing POSS-DMDBS was enhanced, approximately approached to that of iPP containing tri-POSS/DMDBS. The tensile strength of iPP with POSS-DMDBS was significantly increased from 34 MPa to 40 MPa, as high as that of iPP with iso-POSS/DMDBS. The different effects caused by the specific interaction between POSS and DMDBS could possibly be applied in the modification of iPP.     

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。     

反应性多面低聚倍半硅氧烷对聚烯烃的改性研究

带有可反应功能基团的多面低聚倍半硅氧烷(polyhedral oligomeric silsesquioxane,简称POSS),是一类极具应用前景的新型纳米增强剂。本文简要综述了该类纳米增强剂对聚乙烯、聚丙烯、聚苯乙烯、聚降冰片烯的改性研究进展。     

多面体倍半硅氧烷制备有序介孔氧化硅材料

Octa(tetramethylammonium)-polyhedral oligomeric silsesquioxane(TMA-POSS) with cage-like structure was synthesized, the structure was characterized by NMR, FTIR and Elemental analyses. The mesoporous silica was prepared under alkaline condition using TMA-POSS as the silicon source and hexadecyltrimethylammonium bromide (CTAB) as the template, the structures of these products were characterized by XRD, TEM and nitrogen adsorption and desorption methods. The results indicate that the synthesized silica exhibites a well-ordered hexagonal pore structure with larger specific surface area. With increasing of CTAB molar ratio, the spacing of the crystal plane d100 is increased. The effects of the pH values on the mesoporous structure in the reaction system with different molar ratio of nPOSS / nCTAB were investigated. The synthesis mechanism of mesoporous silica was also discussed.     

基于多面体低聚倍半硅氧烷体系的一种独特发光现象

实验发现将2种POSS（多面体低聚倍半硅氧烷）单体氨苯基异丁基POSS和八异丁基POSS置于四氢呋喃搅拌加热后，原来不发光的POSS单体表现出较强的发光。为解释这个发光现象，我们对溶剂处理前后的POSS材料进行了结构和发光性能表征，通过¹HNMR、²⁹Si NMR及红外光谱等方法表征了POSS材料在THF中加热处理前后的结构，实验结果表明，这两种POSS在处理前后结构几乎没有变化，可以保持完整的笼状结构，但处理后的POSS分子¹H NMR谱中含有少量的溶剂峰。FTIR结果也表明处理前后的POSS结构几乎不变；我们也通过XPS表征了处理后的POSS中Si原子的价态，结果表明其价态未发生变化。结合这两种POSS材料处理前后的发光性能以及结构表征结果，我们认为，这种发光现象可能与POSS的吸附效应有关，即溶剂分子进入POSS笼中，形成POSS/溶剂加合物，从而改变了原来的POSS的电子结构，使得相应的POSS材料出现发光现象。     

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。     

A Nanocage for Nanomedicine: Polyhedral Oligomeric Silsesquioxane (POSS)

Ground‐breaking advances in nanomedicine (defined as the application of nanotechnology in medicine) have proposed novel therapeutics and diagnostics, which can potentially revolutionize current medical practice. Polyhedral oligomeric silsesquioxane (POSS) with a distinctive nanocage structure consisting of an inner inorganic framework of silicon and oxygen atoms, and an outer shell of organic functional groups is one of the most promising nanomaterials for medical applications. Enhanced biocompatibility and physicochemical (material bulk and surface) properties have resulted in the development of a wide range of nanocomposite POSS copolymers for biomedical applications, such as the development of biomedical devices, tissue engineering scaffolds, drug delivery systems, dental applications, and biological sensors. The application of POSS nanocomposites in combination with other nanostructures has also been investigated including silver nanoparticles and quantum dot nanocrystals. Chemical functionalization confers antimicrobial efficacy to POSS, and the use of polymer nanocomposites provides a biocompatible surface coating for quantum dot nanocrystals to enhance the efficacy of the materials for different biomedical and biotechnological applications. Interestingly, a family of POSS‐containing nanocomposite materials can be engineered either as completely non‐biodegradable materials or as biodegradable materials with tuneable degradation rates required for tissue engineering applications. These highly versatile POSS derivatives have created new horizons for the field of biomaterials research and beyond. Currently, the application of POSS‐containing polymers in various fields of nanomedicine is under intensive investigation with expectedly encouraging outcomes.

     

Polyhedral Oligomeric Silsesquioxane (POSS) Nanoscale Reinforcement of Thermosetting Resin from Benzoxazine and Bisoxazoline

Summary: The reaction between octaaminophenyl polyhedral oligomeric silsesquioxane (OAPS) and 2,2′‐(1,3‐phenylene)‐bis(4,5‐dihydro‐oxazoles) (PBO) over different temperature ranges was confirmed by FT‐IR spectroscopy. The OAPS was used to modify benzoxazine (BZ) in the presence of PBO. The novel polybenzoxazine (PBZ)‐PBO/OAPS hybrid nanocomposite was prepared by solvent methods. Dynamic mechanical analyses indicated that the nanocomposites exhibited much higher T_g values than the pristine PBZ and PBZ‐PBO resin, and the storage modulus of the nanocomposites was maintained at higher temperatures, although only a small amount of OAPS was incorporated into the systems. Dynamic thermogravimetric analysis showed that the thermal stability of the hybrid was also improved by the inclusion of OAPS.

DMA of PBZ (a), PBZ‐PBO (b), and PBZ‐PBO/OAPS nanocomposites (c–e).     

双(环戊二烯基)二氯化锆催化合成乙烯-笼型倍半硅氧烷杂化共聚物及其结构表征

通过双(环戊二烯基)二氯化锆(Cp₂ZrCl₂)催化剂和改良的甲基铝氧烷(MMAO)助催化剂, 合成了无机-有机杂化共聚物. 研究了2种具有不同单乙烯基反应基团的笼型倍半硅氧烷(POSS)与乙烯的聚合. 对共聚产物的结构、 热力学性质、 分子量及其分布等进行了研究. 共聚单体(POSS)的插入率在0.01%~0.30%之间, 随着共聚单体在共聚物中摩尔分数的增大, 聚合物的熔点和熔解热降低. 共聚物的热重分析结果显示, 乙烯-POSS共聚物拥有更高的热分解温度以及较高的热分解残留量. 随着POSS的加入, 聚合物的分子量明显提高, 聚合物的分子量分布变宽.     

多面体笼型倍半硅氧烷纳米杂化低介电材料的研究

多面体笼型倍半硅氧烷( POSS)是由O-Si-O链接的纳米大小的笼型无机芯[(SiO1.5)n]和外围有机取代基团（活性或惰性）组成,这种独特的结构为杂化功能材料的制备提供了重要的平台与基础。本文从低介电材料结构对性能的影响,以及低介电性能的形成机理,综述了当前低介电材料制备方法,尤其是多面体笼型倍半硅氧烷( POSS)在低介电材料控制制备的研究进展,为该领域新材料设计提供借鉴。     

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.     

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.

     

聚苯乙烯/多面体倍半硅氧烷(POSS)纳米复合材料

本研究通过Wittig反应合成了同时含有金属和双键的新型磁性多面体齐聚倍半硅氧烷POSS1(Fc-CH=CH-C6H6-(C4H9)7Si8O12,Fc:Ferrocene),并通过FTIR1、H-NMR1、3C-NMR2、9Si-NMR对其化学结构进行了表征。将其加入苯乙烯中通过自由基本体聚合制备了聚苯乙烯/POSS1纳米复合材料。XRD和TEM结果表明,POSS1在纳米材料中含量为1%(wt)和3%(wt)时可达分子级分散,而含量为5%(wt)时部分POSS1以晶体形式存在。热失重分析表明PS/POSS1纳米材料较纯PS热稳定性增加,含5%(wt)POSS1的纳米复合材料起始分解温度比纯PS的约提高了19℃。PS/POSS1纳米材料的玻璃化转变温度较纯PS明显提高。     

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.     

硅倍半氧烷改性聚酰亚胺(PI/Si)复合膜性能简

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Tg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.     

Wettability of Polyhedral Oligomeric Silsesquioxane Nanostructured Polymer Surfaces

Summary: Some model structures of waterborne polyurethane anionomers containing various amounts (ca. 3–20%) of a diol functionalized polyhedral oligomeric silsesquioxane (POSS) nanofiller were prepared. X‐ray diffraction showed the formation of a nanocrystalline structure in all copolymers considered. Static contact angle measurements indicated a significant enhancement of surface hydrophobicity as well as reduction in surface tension components even at the least POSS level (3%). Dynamic contact angle cycles allowed the evaluation of the hysteresis, which was found to be large and kinetically increasing in POSS‐modified samples. Film topography was analyzed by AFM, showing a more pronounced roughness in the nanostructured surface.

The AFM image showing a moderate roughness increase.