Synthesis and Luminescent Property of Polycarbazole/Polyhedral Oligomeric Silsesquioxane Nanocomposites

Polyvinylcarbazole（PVK） composites containing organic-inorganic hybrid polyhedral oligomeric silse-squioxane（POSS） PVK-POSS were prepared by free radical polymerization. POSS monomers reacted with vinylcarbazole and were completely dispersed at molecular level in PVK matrix and PVK-POSS nanocomposites display higher glass transition temperature（Tg） in comparison with neat PVK. Optical properties of PVK/POSS nanocomposites were investigated by UV-spectrum and PL-spectrum and the results show that the PVK-POSS nanoparticles have a good interface effect and improve color purity effectively. The maximum absorption wavelength bathochromically shifts gradually with the increasing of the content of POSS. The luminescent intensity becomes higher and higher with the increase of POSS content, and reaches its maximum luminescent intensity when the POSS content is 3% （mass fraction）, while some POSS-rich nanoparticles are present in matrix when contents of POSS are beyond 5%.

Study of Flame Retardation of Polycarbonate Modified by Polyhedral Oligomeric Silsesquioxane and Caged Bicyclic Phosphate

The flame-retarded polycarbonate（PC） has been made with octaphenyl polyhedral silsesquioxane（OPS） and/or caged bicyclic phosphate（Trimer）.Thermal gravimetric analysis（TGA）,Fourier-transform infrared（FTIR）,TGA-FTIR,limiting oxygen index（LOI）,and mechanical tests have been employed to characterize the modified PC.The additives of OPS and Trimer in PC have been proved to be effective flame-retardants because of the synergistic interaction between the elements of P and Si.The role of OPS and Trimer in PC degradation are different：OPS participates in the charring of PC,while Trimer makes PC degrade in advance.In addition,OPS and Trimer induced obvious differences in the mechanical properties of PC.

Fabrication of Layer-by-layer Films of Polyhedral Oligomeric Silsesquioxanes

Layer-by-layer (LBL) self-assembly method was used to fabricate siliceous ultrathin films by using polyhedral oligomeric silsesquioxanes as building blocks. Ammonium salt of octasilsesquioxane acid (OSi8) and poly(diallyldimethylammonium chloride) (PDDA) were alternately assembled onto CaF2 slide to form nanocomposite multilayers. Linear build-up of the LBL films was confirmed by UV-Vis spectroscopy. IR spectrum suggests existence of OSi8 and PDDA in the LBL films. Atomic force microscopic surface topography of the LBL films indicates the OSi8 covers the entire surface of the topmost layer and shows a granular morphology.

Polymer solar cells with an inverted device configuration using polyhedral oligomeric silsesquioxane-[60]fullerene dyad as a novel electron acceptor

A polyhedral oligomeric silsesquioxane-[60]fullerene (POSS-C60) dyad was designed and used as a novel electron acceptor for bulk heterojunction (BHJ) polymer solar cells (PSCs) with an inverted device configuration. The studies of time-resolved photoinduced absorption of the pristine thin film of poly[(4,4'-bis(2-ethylhexyl)dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-(4,7-bis (2-thienyl)-2,1,3-benzothiadiazole)-5,5'-diyl] (SiPCPDTBT) and the composite thin film of SiPCPDTBT:POSS-C60 indicated efficient electron transfer from SiPCPDTBT to POSS-C60 with inhibited back-transfer. BHJ PSCs made by SiPCPDTBT mixed with POSS-C60 yielded the power conversion efficiencies (PCEs) of 1.50%. Under the same operational conditions, PCEs observed from BHJ PSCs made by SiPCPDTBT mixed with [6,6]-phenyl-C61-butyric acid methyl ester were 0.92%. These results demonstrated that POSS-C60 is a potentially good electron acceptor for inverted BHJ PSCs.

Ultrasmall Nanoparticle ROS Scavengers Based on Polyhedral Oligomeric Silsesquioxanes

Although tremendous efforts have been devoted to the structural and functional tailoring of natural polyphenol-functionalized nan oparticles,preparing ultrasmall sized(<6 nm)particles with precisely-defined structures has remained a grand challenge.In this work,we reported the preparation of ultra-small and precisely structured polyhedral oligomeric silsesquioxanes(POSS)-based polyphenol nanopartides(T8^-,T10^-,and T12^-GAPOSS)by accurately functionalizing the POSS surface with plant polyphenol gallic acid units via thiol-Michael"click"reactions.Those polyphenol nanoparticles exhibited strong free radical scavenging capacity,good biocompatibility and ability to resist cell oxidative damage,which dem on strated great potentials in inhibiting oxidative stress in duced pathologies.

Effectiveness of an ocular adhesive polyhedral oligomeric silsesquioxane hybrid thermo-responsive FK506 hydrogel in a murine model of dry eye

Dry eye is a common ocular disease that results in discomfort and impaired vision,impacting an individual’s quality of life.A great number of drugs administered in eye drops to treat dry eye are poorly soluble in water and are rapidly eliminated from the ocular surface,which limits their therapeutic effects.Therefore,it is imperative to design a novel drug delivery system that not only improves the water solubility of the drug but also prolongs its retention time on the ocular surface.Herein,we develop a copolymer from mono-functional POSS,PEG,and PPG(MPOSS-PEG-PPG,MPEP)that exhibits temperature-sensitive sol-gel transition behavior.This thermo-responsive hydrogel improves the water solubility of FK506 and simultaneously provides a mucoadhesive,long-acting ocular delivery system.In addition,the FK506-loaded POSS hydrogel possesses good biocompatibility and significantly improves adhesion to the ocular surface.In comparison with other FK506 formulations and the PEG-PPG-FK506(F127-FK506)hydrogel,this novel MPOSS-PEG-PPG-FK506(MPEP-FK506)hydrogel is a more effective treatment of dry eye in the murine dry eye model.Therefore,delivery of FK506 in this POSS hydrogel has the potential to prolong drug retention time on the ocular surface,which will improve its therapeutic efficacy in the management of dry eye.

Synthesis of peptide dendrimers with polyhedral oligomeric silsesquioxane cores via click chemistry

Inorganic polyhedral oligomeric silsesquioxane （POSS） was used as the core for the synthesis of poly（t- lysine） peptide dendrimer via copper-catalyzed azide-alkyne click chemistry. The inorganic/organic composite dendrimer was characterized by MS, 1H NMR, FTIR, GPC and DLS.

Bridged polyhedral oligomeric silsesquioxane(POSS):A potential member of silsesquioxanes

Two novel and well-defined polyhedral oligomeric silsesquioxanes（POSS） with two same Si_8O_（12） cores and a reactive NH group, namely bridged-POSS（2a and 2b）,have been prepared by the traditional ＇corner-capping＇ reaction.X-ray diffraction demonstrates that those two POSS have the similar T_8 structure.From the thermo-gravimetric analysis,bridged-POSS shows the belter thermal degradation stability than the contrastive POSS.

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

Isotactic polypropylene（iPP） was modified by the introduction of polyhedral oligomeric silsesquioxanes（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 crystal!inity 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.

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.

Facile generation of highly durable thiol-functionalized polyhedral oligomeric silsesquioxane based superhydrophobic melamine foam

In this study,a durable superhydrophobic/superoleophilic melamine foam was fabricated by a facile and rapid one-step thiol-ene click chemistry and Michael addition reaction,which demonstrated excellent robustness in oil/water separation.First,1H,1H,2H-perfluoro-1-hexene reacted with thiol-functionalized polyhedral oligomeric silsesquioxane via the thiol-ene click chemistry to obtain a fluorinated thiol-functionalized polyhedral oligomeric silsesquioxane solution.Subsequently,the melamine foam was immersed to the solution system to form nanoaggregates on the melamine foam surface by the Michael addition reaction in the presence of ultraviolet light.The micro/nano rough structure and low surface energy of the nanoaggregates layer endowed the pristine melamine foam with superhydrophobicity;the water contact angle was greater than 150°.More importantly,the as-prepared melamine foam could withstand harsh conditions,such as a corrosive solution environment,strong ultraviolet light,mechanical compression,high and low temperature exposure,and ultrasonic washing.Driven by gravity,the as-prepared melamine foam could efficiently separate the oil/water mixtures and maintain 98%separation efficiency at high and low temperatures.In addition,it maintained the desirable absorption capability in different oil/organic solvents even after 15 absorption cycles.Accordingly,this facile,low-cost,and robust onestep method provides important support for the superhydrophobic oil/water separation field.

聚硅氧烷-聚酰亚胺复合材料抗原子氧侵蚀机理分子动力学研究

为了探究不同取代基聚硅氧烷提升聚酰亚胺在太空环境中抵抗原子氧(AO)侵蚀能力的作用机制,本研究采用反应分子动力学(MD)模拟,分析了取代基分别为三氟甲基(-CF_(3))和甲基(-CH_(3))的多面体笼型聚硅氧烷(POSS)复合聚酰亚胺纳米材料的抗原子氧侵蚀性能。结果表明:PI/CH_(3)-POSS和PI/CF_(3)-POSS复合材料均表现出较强的抗AO侵蚀能力,其作用机制是通过形成SiO_(2)层以阻止AO向聚合物基体的传播和热量的传递,其中PI/CF_(3)-POSS复合材料的效果最优,经35 ps的AO侵蚀模拟后其归一化质量为0.83,而PI/CH_(3)-POSS复合材料的归一化质量为0.78。

左旋氨氯地平分子印迹聚合物的合成及性能研究

采用烯丙基DESs和有机-无机杂化纳米材料POSS作为功能单体,利用两者的协同作用成功制备了氨氯地平分子印迹聚合物。通过优化DESs和POSS的比例,对S-AML的吸附量达到12.8μg/mg,以及印迹因子为6.95。并分别使用Langmuir模型和Freundlich模型对吸附等温线进行拟合,发现MIP的吸附过程更符合Langmuir模型。评价了MIP对血浆加标样品的固相萃取性能,对S-AML的最高回收率可达92.9%。实验结果表明,DESs和POSS的联合使用提高了印迹聚合物对S-AML的选择性和吸附性能。

透明聚酰亚胺复合薄膜的制备及性能研究

采用八氨基苯基聚倍半硅氧烷(OA-POSS)对Al_(2)O_(3)微球表面进行修饰,再将改性Al_(2)O_(3)均匀分散在以氢化均苯四甲酸二酐(HPMDA)、4,4′-(六氟异丙烯)二酞酸酐(6FDA)、4,4′-二氨基二苯醚(ODA)为单体制备的无色透明聚酰亚胺(CPI)薄膜中。通过傅里叶变换红外光谱仪、紫外-可见分光光度计、导热系数测试仪、热重分析仪等对透明复合薄膜进行表征。结果表明:透明复合薄膜在保持良好机械性能的同时(拉伸强度在92MPa以上),在可见光区仍拥有较高的透光率(透光率超过82%),而且在低Al_(2)O_(3)负载量下,透明复合薄膜的热稳定性、导热性能得到明显改善;制备的透明复合薄膜可作为柔性显示器件的衬底材料以及电子封装材料。

本征抗原子氧聚酰亚胺超细纤维膜的制备与性能研究

为应对空间探索活动对本征抗原子氧聚酰亚胺超细纤维膜的需求,文章将Si元素与P元素引入到聚酰亚胺分子结构中,采用静电纺丝技术制备了本征抗原子氧聚酰亚胺超细纤维膜。系统研究了Si元素与P元素的引入对超细纤维的化学结构、微观形貌、光学性能、热性能以及抗原子氧侵蚀性能的影响。结果表明:分子结构中引入Si元素和P元素的聚酰亚胺超细纤维膜表面光滑,微观结构呈现连续的纤维状;玻璃化转变温度(T_(g))大于290℃,450℃以下时均表现出良好的热稳定性;且由于引入了Si元素和P元素,在经积分通量为2.0×10^(21) atom/cm^(2)的原子氧辐照后,聚酰亚胺超细纤维膜的原子氧侵蚀速率与Kapton®相比降低了1个数量级。

POSS基两亲性嵌段共聚物的合成及自组装行为

用不同结构三乙氧基硅烷为原料,通过水解缩合和环氧化的方法合成了环氧基苯基低聚笼型倍半硅氧烷,再利用胺基和环氧开环反应与聚醚胺反应合成POSS基嵌段共聚物(PEA-POSS),最后将苯基结构羧酸化合成两亲性嵌段共聚物(PEA-POSS-COOH)。利用傅里叶变换红外光谱(FT-IR)和核磁共振氢谱(1H-NMR)表征了PEA-POSS-COOH的化学结构。采用溶剂挥发诱导法促使PEA-POSS-COOH自组装,形成以疏水POSS为核、亲水PEA链为壳的球形胶束。利用扫面电子显微镜(SEM)、能量分散型X射线光谱(EDS)、动态激光光散射(DLS)、小角X射线散射仪(XRD)和差示扫描量热仪(DSC)表征了组装体的形貌与结构性能。结果表明,POSS基两亲性嵌段聚合物可组装成粒径约1.14μm的球形胶束,且POSS结构中的π-π堆叠作用使得球形胶束具有较为稳定结构,熔点提高。

碳钢表面低聚倍半硅氧烷复合氟锆酸转化膜的耐蚀性研究

为提高碳钢表面的耐腐蚀性,采用氟锆酸复合氨基/羟基-多面体低聚倍半硅氧烷(NH_(2)/OH-POSS)制备了无磷无铬的氟锆酸复合低聚倍半硅氧烷转化膜。使用盐水浸泡、电化学测试、扫描电镜(SEM)和X射线光电子能谱(XPS)对复合膜的耐蚀性、表面形貌及成分进行了表征。结果表明:氟锆酸溶液复合氨基/羟基-多面体低聚倍半硅氧烷水溶液的最佳工艺为1.2 g/L氟锆酸、4.5 g/L低聚倍半硅氧烷,pH值为4、温度30℃、钝化时间2 min;盐水浸泡试验和电化学测试结果表明,复合转化膜较纯氟锆酸转化膜的防腐性得到明显改善;SEM结果表明,低聚倍半硅氧烷的加入弥补了氟锆酸膜层的裂痕和孔洞的缺陷,使膜层更加致密;XPS结果表明,低聚倍半硅氧烷和氟锆酸共同参与转化膜的形成。

多孔硅基复合材料的可控制备及其应用于锂电池负极材料的研究

将苯基和乙烯基两种不完全缩合的倍半硅氧烷硅醇锂与聚丙烯腈(PAN)复合,利用Friedel-Crafts反应制备多孔结构,后经高温碳化制备成多孔硅基负极材料。采用扫面电子显微镜(SEM)和N2吸脱附测试,表征了材料的多孔结构,并在LAND电池测试系统上对样品负极进行连续充放电测试。结果表明:所制备的多孔硅基复合材料具备良好的多孔结构,孔径约4 nm;在应用到锂离子电池负极后,其首圈库伦效率高达78.5%,在200次循环后能够保持665.2 m Ah/g的放电比容量,容量保持率达到87.9%;即使在2 A/g的高电流密度下,可逆比容量仍然能够保持318.3 m Ah/g。

低聚倍半硅氧烷在钢铁防腐环氧涂层中的应用

重点综述了多面体低聚倍半硅氧烷(POSS)结构特征、引入环氧涂层的方式、对环氧涂层防腐性能的影响。POSS独特的无机核/有机壳结构,对有机基团的可裁剪性、相容性和反应性为设计具有多种功能的POSS/环氧防腐涂层提供了可能。POSS可以通过自身为主体结构或修饰其他主体结构的方式引入到环氧涂层中。POSS的引入能有效提高环氧涂层的防腐性能,其原因可能主要在于POSS纳米笼的物理填充屏蔽作用、增强环氧网络的交联致密化作用、发挥电活性特征促进稳定钝化层的形成与主动修复作用。未来应加强探索POSS引入环氧树脂的新方式,控制POSS结构的分散均匀性,深入揭示POSS与环氧树脂的相互作用机理以及寻求更多阐释POSS提高涂层防腐性能的直观证据。

苯基乙烯基低聚硅倍半氧烷的合成及乙烯基酯树脂复合物的性能

以苯基三甲氧基硅烷和甲基丙烯酰氧基丙基三甲氧基硅烷为原料,制备了苯基乙烯基低聚硅倍半氧烷(MPOSS),采用^(1)H-NMR,^(13)C-NMR,^(29)Si-NMR和MALDI-TOF-MS证明MPOSS段主体为完整的T10和T12笼型结构。将MPOSS用于乙烯基酯树脂(VER)制备了VER/MPOSS复合物,热重分析、差示扫描量热分析和力学性能测试表明,VER/MPOSS复合物的热稳定性和玻璃化转变温度随MPOSS比例增加而升高;相对于纯VER,添加20%的MPOSS后复合物的弯曲强度、弯曲模量和断裂力分别提高了203%,365%和200%,力学性能显著提升。极限氧指数、锥形量热、热重-红外等阻燃性能与机理研究表明,MPOSS促进了致密炭层的形成,阻止了有机挥发性产物的释放,降低了VER的热释放、烟释放和有毒气体释放量,增强了VER/MPOSS复合物的阻燃性能。综合认为,MPOSS同时提高了乙烯基酯树脂的力学性能、阻燃性能和综合性能。