Properties of nanoporous organosilicate hybrid thin films with a bimodal pore size distribution

Low dielectric poly[methylsilsesquioxane‐ran‐trifluoropropylsilsesquioxane‐ran‐(2,4,6,8‐tetramethyl‐2,4,6,8‐tetraethylenecyclotetrasiloxane)silsesquioxane]s {P[M‐ran‐TFP‐ran‐(TCS)]SSQs} having various compositions were synthesized using trifluoropropyl trimethoxysilane, methyl trimethoxysilane and 2,4,6,8‐tetramethyl‐2,4,6,8‐tetra(trimethoxysilylethyl)cyclotetrasiloxane. The chemical composition of the polymers and the content of SiOH end‐groups were controlled by adjusting the reaction conditions, and they were characterized by ¹H‐NMR. The thermally decomposable trifluoropropyl groups on the P[M‐ran‐TFP‐ran‐(TCS)]SSQ backbone and heptakis(2,3,6‐tri‐O‐methyl)‐β‐cyclodextrin (CD) were employed as pore generators. The dielectric constants of the porous CD/P[M‐ran‐TFP‐ran‐(TCS)]SSQ films were in the range 2.0–2.7 (at 100 kHz) depending on the concentration of the porogens, and showed no change over 4 days under aqueous conditions. The pore size of the films showed a bimodal distribution, with diameters of ca 0.5–1.0 nm for those originating from the trifluoropropyl groups and 1.7 nm from the CD. The elastic modulus and hardness of the 30 vol% CD‐blended film with a dielectric constant of 2.26 were 2.40 and 0.38 GPa, respectively, as determined by a nanoindenter. Copyright © 2005 Society of Chemical Industry     

聚碳酸酯与硅倍半氧烷复合物气相热裂解和凝聚相产物对比

采用实验室自制的笼型八苯基硅倍半氧烷(OPS)和一种新型阻燃剂含磷笼型低聚硅倍半氧烷(DOPO-POSS),通过双螺杆挤出机加工的方式与聚碳酸酯(PC)共混制得质量分数4%DOPO-POSS和6%OPS的阻燃复合物。利用裂解-气相色谱/质谱联用仪(Py-GC/MS)对复合物的裂解产物进行了分析;通过傅里叶变换红外光谱仪(FT-IR)和扫描电子显微镜-X射线能谱仪(SEM-EDS)分别对残炭的凝聚相结构与元素组分进行分析。Py-GC/MS分析结果表明,总的质谱图显示PC/DOPO-POSS和PC/OPS复合物在热解过程中释放出大量小分子气体产物,有效地促进了炭层的膨胀;OPS在气相裂解中释放出大量的苯和气态Si O2,并有少量CO2气体释放;DOPO-POSS裂解过程中释放出多种小分子气体,其中DOPO含量最高,达到26%。FT-IR对凝聚相炭层结构测试表明,PC/OPS和PC/DOPO-POSS复合物的内部炭层结构相似,由无机炭结构组成;在外部炭层结构中,PC/OPS复合物含有大量-O-Si-O-结构,并伴随有少量的芳香烃炭结构和Si-C结构;PC/DOPO-POSS复合物主要由-P(=O)-O-Si-结构和少量Si-O结构组成。SEM-EDS测试结果表明,PC/DOPO-POSS复合物炭层成分中C元素含量最高,O元素含量次之,Si和P元素含量最少;PC/OPS复合物炭层成分中,Si和O元素含量最大,占到92.5%,C元素含量最低。     

亚磷酸酯功能化聚硅氧烷扩链聚乳酸的阻燃性能研究

将聚氨基环氧基硅氧烷（PSQ）以及亚磷酸酯功能化的聚氨基环氧基硅氧烷（PPSQ）与聚乳酸（PLA）通过熔融共混制备了扩链PLA。研究了亚磷酸酯基团的引入对PSQ在PLA中的扩链和阻燃性能的影响,探究PPSQ在PLA中的阻燃机理。结果表明,相比于PSQ,PPSQ可以明显提高PLA的分子量和复合黏度,具有更好的扩链作用;PPSQ的引入可以明显改善PLA的阻燃性能,使得PLA?PPSQ的极限氧指数提高至25.4 %,比纯PLA提升了31.6 %,且使得PLA的热释放速率峰值和总热释放量分别下降了18.1 %和16.6 %。分析可知,由于亚磷酸酯基团的引入,促使PLA?PPSQ中的硅元素在燃烧过程中向炭层表面迁移形成更多富含碳化硅和氧化硅的致密炭层,起到隔热隔氧的作用,进而发挥优异的阻燃性能。     

有机硅阻燃剂在聚酯中的应用研究进展

文章综述了聚二甲基硅氧烷(PDMS)、聚倍半硅氧烷(POSS)和硅树脂等有机硅类阻燃剂在聚酯中的应用研究进展,展望了有机硅阻燃剂的应用前景。     

Redox-Responsive Porphyrin-Based Polysilsesquioxane Nanoparticles for Photodynamic Therapy of Cancer Cells

The development of stimulus-responsive photosensitizer delivery systems that carry a high payload of photosensitizers is of great importance in photodynamic therapy. In this study, redox-responsive polysilsesquioxane nanoparticles (PSilQNPs) built by a reverse microemulsion approach using 5,10,15,20-tetrakis(carboxyphenyl) porphyrin (TCPP) silane derivatives as building blocks, were successfully fabricated. The structural properties of TCPP-PSilQNPs were characterized by dynamic light scattering (DLS)/ζ-potential, scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). The photophysical properties were determined by UV-vis and fluorescence spectroscopy. The quantity of singlet oxygen generated in solution was measured using 1,3-diphenylisobenzofuran. The redox-responsive release of TCPP molecules was successfully demonstrated in solution in the presence of a reducing agent. The internalization of TCPP-PSilQNPs in cancer cells was investigated using laser scanning confocal microscopy. Phototoxicity experiments in vitro showed that the redox-responsive TCPP-PSilQNPs exhibited an improved phototherapeutic effect on cervical cancer cells compared to a non-responsive TCPP-PSilQNP control material.     

有机桥连聚倍半硅氧烷光学防潮涂层的制备

以巯丙基三甲氧基硅烷(MPTMS)和3-(甲基丙烯酰氧)丙基三甲氧基硅烷为(MATMS)为原料,经巯-烯点击反应制备有机桥连硅烷前驱体3-三甲氧硅基丙基-2-甲基-3-[(3-三甲氧硅基)丙基硫代]丙酸酯(MPMA).采用溶胶-凝胶法,MPMA在酸性条件下水解-缩聚得到溶胶,将其分别沉积在载玻片和聚醚酰亚胺(PEI)上...     

Poly(acetoxystyrene-co-isobutylstyryl POSS) Nanocomposites: Characterization and Molecular Interaction

The poly(acetoxystyrene-co-isobutyl styryl polyhedral oligomeric silsesquioxanes)s (PAS-POSS) were synthesized by free radical polymerization and characterized by FTIR, high resolution NMR, FTIR, GPC, and DSC. The results show that the POSS content can be controlled by varying the POSS feed ratios. The interactions between organic components and inorganic POSS core, and the effects of inorganic POSS core on the properties of the resulting hybrids were investigated by high resolution solid state ¹³C NMR, ²⁹Si NMR and FTIR spectra. The results provide detailed understandings of the effects of POSS moiety on properties of hybrid polymers.     

Biodegradable Polysilsesquioxane Nanoparticles as Efficient Contrast Agents for Magnetic Resonance Imaging

Polysilsesquioxane (PSQ) nanoparticles are crosslinked homopolymers formed by condensation of functionalized trialkoxysilanes, and provide an interesting platform for developing biologically and biomedically relevant nanomaterials. In this work, the design and synthesis of biodegradable PSQ particles with extremely high payloads of paramagnetic Gd(III) centers is explored, for use as efficient contrast agents for magnetic resonance imaging (MRI). Two new bis(trialkoxysilyl) derivatives of Gd(III) diethylenetriamine pentaacetate (Gd‐DTPA) containing disulfide linkages are synthesized and used to form biodegradable Gd‐PSQ particles by base‐catalyzed condensation reactions in reverse microemulsions. The Gd‐PSQ particles, PSQ‐ 1 and PSQ‐ 2 , carry 53.8 wt% and 49.3 wt% of Gd‐DTPA derivatives, respectively. In addition, the surface carboxy groups on the PSQ‐ 2 particles can be modified with polyethylene glycol (PEG) and the anisamide (AA) ligand to enhance biocompatibility and cell uptake, respectively. The Gd‐PSQ particles are readily degradable to release the constituent Gd(III) chelates in the presence of endogenous reducing agents such as cysteine and glutathione. The MR relaxivities of the Gd‐PSQ particles are determined using a 3T MR scanner, with r₁ values ranging from 5.9 to 17.8 mMs^?1 on a per‐Gd basis. Finally, the high sensitivity of the Gd‐PSQ particles as T₁‐weighted MR contrast agents is demonstrated with in vitro MR imaging of human lung and pancreatic cancer cells. The enhanced efficiency of the anisamide‐functionalized PSQ‐ 2 particles as a contrast agent is corroborated by both confocal laser scanning microscopy imaging and ICP‐MS analysis of Gd content in vitro.     

复合型低介电常数聚酰亚胺复合材料研究进展

聚酰亚胺具有优异的力学性能及耐热性,一直是微电子产业的重要电介质材料之一。近年来,随着微电子行业的发展和5G通讯技术的兴起,从能耗要求到信号接收等方面都对降低聚酰亚胺的介电常数和介电损耗提出更高的要求。如何在保留聚酰亚胺优异性能的同时尽可能降低其介电常数与损耗是目前亟需解决的问题。本文综述了近年来多孔聚酰亚胺和聚合物填料、无机纳米填料复合改性聚酰亚胺等复合型低介电聚酰亚胺的研究及应用进展,探讨了如何在降低聚酰亚胺介电常数的同时保持其他性能,并对其发展进行了展望,为新型复合型低介电聚酰亚胺材料的设计与制备提供新思路。     

不同有机官能团聚硅氧烷微球的制备与表征

以乳液聚合法制备粒径分布均匀、球形度良好的聚甲基硅氧烷微球(MPSQ)、聚乙烯基硅氧烷微球(VPSQ)、聚巯丙基硅氧烷微球(MPPSQ),采用SEM、DLS、FT-IR、XRD、TGA、接触角等测试技术对微球的微观形貌、粒径大小及分布、聚集态结构、耐热性、疏水性等进行了表征。研究结果表明,有机基团对微球的耐热性与疏水性有重要影响,MPSQ和VPSQ的耐热性优于MPPSQ,疏水性从高到低依次为:MPSQ>VPSQ>MPPSQ。聚硅氧烷微球的形成过程可能是单体首先在催化剂的作用下,水解生成硅醇,硅醇开始缩聚形成核,之后通过吸取溶液的硅醇,不断成长,最终形成微球,其中同时存在核生成和核生长,两过程相互竞争,哪个过程占优势取决于反应条件。提高反应温度,使得核生成占优势,最终生成的微球粒径变小,单分散性变差。