二步法合成乙烯基八聚笼型倍半硅氧烷

采用正硅酸乙酯和四甲基氢氧化铵为原材料,合成了八聚四甲基铵基笼型倍半硅氧烷;采用二甲基乙烯基氯硅烷对其进行乙烯基取代,得到含乙烯基的八聚笼型倍半硅氧烷。采用核磁共振硅谱29Si-NMR、红外光谱IR和凝胶渗透色谱GPC对其结构进行了分析。     

乙烯基笼型倍半硅氧烷的合成及表征

分别采用乙烯基三甲氧基硅烷和乙烯基三乙氧基硅烷为原料,盐酸作为催化剂,通过水解缩合反应合成了乙烯基笼型倍半硅氧烷,探讨了温度、盐酸和去离子水的配比、溶剂用量和聚合时间对实验产率的影响。并通过红外和核磁共振氢谱/碳谱等手段对产物进行了表征。结果表明:合成的化合物为乙烯基笼型倍半硅氧烷。同时,热失重分析表明,失重5%对应的温度在244.1℃,说明产物的热稳定性很高。     

笼型倍半硅氧烷的合成与应用

笼型倍半硅氧烷(POSS)是一种新型有机硅杂化材料,在耐高温材料、阻燃材料以及高分子增强材料方面具有广阔的发展前景.主要介绍了苯基、氨基、环氧基和甲基等4种官能团取代笼型倍半硅氧烷的合成方法及影响因素、性能和应用前景.     

笼型八聚(二甲基硅氧基)倍半硅氧烷的合成及其对硅橡胶复合材料性能的影响

将实验室自制的笼型八聚(二甲基硅氧基)倍半硅氧烷作为乙烯基硅橡胶的交联剂,再添加补强填料白炭黑和耐热填料纳米Fe_2O_3,制备出一种耐高温硅橡胶复合材料。通过傅里叶变换红外光谱仪、核磁共振氢谱仪对笼型八聚(二甲基硅氧基)倍半硅氧烷进行结构表征。结果表明,当乙烯基硅油中Si—Vi与笼型八聚(二甲基硅氧基)倍半硅氧烷交联剂中Si—H的摩尔比为1∶1,白炭黑质量分数为20%,硅树脂质量分数为10%,纳米Fe_2O_3质量分数为8%时,硅橡胶复合材料的耐热温度达到470.68℃,剪切强度可达到0.92MPa,拉伸强度为0.99MPa。     

由二氧化硅低温合成可聚合倍半硅氧烷的研究

以无定形二氧化硅(SiO2)为基本原料,经过系列反应成功合成了带有甲基丙烯酸酯基团的笼形倍半硅氧烷。采用红外光谱、差示扫描量热等分析方法对各步反应产物进行了表征。结果表明,所合成的倍半硅氧烷带有可聚合的不饱和基团且具有笼形核/壳结构。可聚合的笼形倍半硅氧烷为具有特殊杂化结构聚合物的合成和应用奠定了基础。     

杂化笼形聚倍半硅氧烷的结构性能与应用

笼形倍半硅氧烷是一类新型高性能的多面体有机／无机分子复合物。本文从笼型倍半硅氧烷的结构特点,合成方法及主要性能方面出发,对笼型倍半硅氧烷的有机／无机杂化改性进行了综合性描述,介绍了它们的发展趋势。     

双功能基多面体低聚倍半硅氧烷(POSS)的合成与表征

以无水乙醇为溶剂,将乙烯基三甲氧基硅烷和甲基三甲氧基硅烷在酸性条件下进行共水解共缩聚反应合成二乙烯基六甲基八聚笼型倍半硅氧烷。讨论了影响反应的各种因素,得出了该反应的最佳条件,在单体浓度为0.35 mol/L,催化剂浓度为0.4 mol/L,水与单体物质的量比为6时,于50℃反应40 h得到的产物有最高的产率。利用红外、核磁共振(1H-NMR、29S-i NMR)和X射线衍射(XRD)对其结构进行了表征,结果证明,产物形成了完整的笼型结构,产物的结构式为[Si8O12(CH=CH2)2(CH3)6],XRD测试也表明产物具有较好的结晶性。     

聚苯基倍半硅氧烷研究进展

分别介绍了梯型、笼形聚苯基倍半硅氧烷及其共聚物的结构、性质和合成方法,重点综述了苯基倍半硅氧烷共聚物研究进展,并对苯基倍半硅氧烷材料的发展趋势进行了展望。     

四羟基多面体倍半硅氧烷/环氧树脂复合体系的制备及性能研究

采用环己基三氯硅烷为反应物,乙腈为溶剂,通过水解缩合反应合成出纯净的环己基六聚笼型倍半硅氧烷,通过FT-IR,(29)Si-NMR对其结构等进行了表征;通过将合成的环己基笼型硅氧烷进行水解,生成了一种新的带有稳定羟基的硅氧烷,并对产物进行了表征;用带有稳定羟基的硅氧烷对环氧树脂进行改性,并对所形成的复合材料的热稳定性、...     

八氯丙基多面体低聚倍半硅氧烷的合成与表征

以工业化的γ-氯丙基三甲氧基硅烷为原料,在浓盐酸为催化剂的条件下制备了八氯丙基多面体低聚倍半硅氧烷(OCPS).研究了反应温度、反应物的投料比对产物收率的影响.得到了最佳合成产物的条件:在40℃的反应温度下,水解缩合20天,γ-氯丙基三甲氧基硅烷、浓盐酸、甲醇的体积比为5:4:100时产率最高,达到28.5%,并对产物结构进行了1HNMR、13CNMR、29SiNMR、FT-IR、GPC表征.     

Dispersions of carbon nanotubes/polyhedral oligomeric silsesquioxanes hybrids in polymer: the mechanical,electrical and EMI shielding properties

A hybrid was synthesized by grafting polyhedral oligomeric silsesquioxane (POSS) to multiwalled carbon nanotubes (MWCNTs). The MWCNT/polymer composites produced using silsesquioxane grafted MWCNTs as a filler had a high electromagnetic interference shielding effectiveness. Homogeneous dispersion of silsesquioxane grafted MWCNTs occurred throughout the polymer without any aggregation, while a pristine MWCNT aggregate that integrated several nanotube domains existed in the polymer matrix. A comparative study of the optical transmittance, electrical, and electromagnetic interference shielding properties of poly(l-lactide) (PLLA)/MWCNT composites based on pristine MWCNTs and silsesquioxane grafted MWCNTs was carried out. A high electromagnetic interference shielding effectiveness (15–16 dB) was obtained in the 36–50 GHz range at a relatively low filler loading (4 wt%) in the PLLA/silsesquioxane grafted MWCNT composite.     

聚(3-羟基丁酸酯-co-4-羟基丁酸酯)/POSS共混体系的性能

采用熔融模压法分别制备了聚(3-羟基丁酸酯-co-4-羟基丁酸酯)[P(3HB-co-4HB)]和两种多面体笼型硅氧烷(POSS)[八异丁基倍半硅氧烷(OIBS)和八氨基苯基倍半硅氧烷(OAPS)]的共混物,考察了不同含量的OIBS,OAPS对共混体系性能的影响。结果表明,两种POSS都起到成核剂的作用。OIBS,OAPS的质量分数小于1%时,可以提高体系结晶温度,力学性能;随着OIBS,OAPS质量分数的提高,成核性有所增加,但因分散性变差,体系热稳定性和力学性能变差。由于OAPS的活泼氨基可与P(3HB-co-4HB)发生化学反应,改性效果较OIBS优。     

Triphenyl benzene-bridged fluorescent silsesquioxane: shape-controlled hybrid silicas by hydrolytic conditions

A new silsesquioxane molecule was synthesized, in which triphenyl benzene was connected with three Si(OC2H5)3 groups using three urea groups as the bridge. The molecule could self-assemble through the intermolecular H-bonding among urea groups and pi-pi interaction of triphenyl benzene core in the solution and it could also be transferred into hybrid silicas by hydrolysis. When the non-preorganized silsesquioxane was hydrolyzed, isolated spherical hybrid silica was gained. However, when the silsesquioxane was preorganized before the hydrolyzation uniform interconnected spherical hybrid silica and intertwined nanofibrous one could be generated under acidic and basic conditions, respectively. The photoluminescence (PL) spectra of the obtained hybrid silicas showed that they still kept the emission properties of their precursor silsesquioxane, and the shift of the emission bands was due to the pi-pi interaction of triphenyl benzene in the course of polycondensation.     

共价功能化POSS/PDMS防腐复合涂层的研究

首先采用硅烷偶联剂通过水解缩合反应方法合成氨基功能化倍半硅氧烷(POSS-NH₂),利用其表面氨基通过表面接枝聚合方法在倍半硅氧烷表面接枝磺化聚苯胺以实现其共价功能化,将磺化聚苯胺功能化倍半硅氧烷和聚二甲基硅氧烷通过溶液共混,利用滴涂法在Q235钢材表面制备出疏水防腐涂层。通过核磁共振(NMR)和傅里叶转换红外光谱(FT-IR)对氨基功能化倍半硅氧烷和磺化聚苯胺功能化倍半硅氧烷的结构进行表征分析;利用光电子能谱(XPS)分析磺化聚苯胺功能化倍半硅氧烷的化学组成和元素含量比例;利用扫描电子显微镜(SEM)表征磺化聚苯胺功能化倍半硅氧烷的微观形貌,观察到表面形貌较规整、呈颗粒状、纤维较粗的结构;采用静态接触角测试分析了四种涂层的疏水性,制备出的共价功能化POSS/PDMS防腐复合涂层疏水性最佳,接触角达到115°;采用EIS电化学阻抗谱和Tafel极化曲线测试表征了四种涂层的耐腐蚀性能,结果表明:共价功能化POSS/PDMS防腐复合涂层的腐蚀电位更大,腐蚀电流密度较小,由此表明所制备的材料具有优异的防腐性能。并且发现涂层的接触角越大,防腐性能越好。     

POSS/聚丙烯腈星型纳米复合物的制备及热性能

通过自由基聚合的方法,将八乙烯基多面笼形低聚倍半硅氧烷(POSS)与丙烯腈(AN)共聚合得到不同POSS含量的AN与POSS的共聚物(PAN-POSS)。采用傅立叶红外光谱(FT-IR)、硅核磁共振(~(29)Si-NMR)、X射线衍射(XRD)、热失重分析(TGA)和差示扫描量热(DSC)对PAN-POSS共聚物结构和性能进行了表征。研究结果表明,POSS笼形结构以化学键合的方式分子水平上均匀地分散在杂化聚合物中,形成了星型结构POSS/聚丙烯腈纳米复合物,复合物中POSS的含量随着反应单体中POSS配比的增加而增加,复合物的热性能随POSS含量增加明显提高。     

Influence of fibre surface oxidation–reduction followed by silsesquioxane coating treatment on interfacial mechanical properties of carbon fibre/polyarylacetylene composites

Carbon fibre was treated with oxidation–reduction followed by silsesquioxane coating method to improve the interfacial properties of carbon fibre/polyarylacetylene (CF/PAA) composites. The treatment method was divided into three phases, i.e., oxidation with oxygen plasma, reduction with LiAlH₄, and coating treatment with vinyl silsesquioxane (VMS–SSO). The fibre surface composition and functional group were analyzed using X-ray photoelectron spectroscopy (XPS). The polar functional groups, especially C–OH which could react with Si–OH on silsesquioxanes, were increased after redox reaction. VMS–SSO coating treatment imported vinyl groups which could react with PAA resin during PAA cure process. The surface morphology of carbon fibre was observed by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The mechanical interfacial properties of the CF/PAA composites were characterized by short-beam bending testing method. Interlaminar shear strength (ILSS) of the CF/PAA composites in different treatment phases were increased by 31.7%, 28.8%, and 59.3%, respectively. The conclusion that oxidation–reduction followed by silsesquioxane coating treatment is an effective method to improve the interfacial properties of the CF/PAA composites can be drawn. This method can be used in other resin systems if the functional groups on silsesquioxane are changed according to those in resins.     

环氧树脂/笼型倍半硅氧烷纳米复合材料的阻燃性能与热解机理

探讨了环氧树脂(EP)/笼型倍半硅氧烷(POSS)纳米复合材料的阻燃性能与热降解机理。利用锥形量热计研究了EP以及EP/POSS的燃烧行为,发现POSS可有效降低EP的热释放速率峰值以及总热释放。热失重-红外联用测试结果表明,虽然EP与EP/POSS热裂解产物种类相似,但EP/POSS气相产物均出现在较高温度下,这是由于POSS的存在延迟了EP热解产物的释放,并且在高温下形成了稳定性良好的含硅杂化炭层。此炭层可有效阻止热量与氧传递,从而在燃烧的过程中阻止下部材料进一步燃烧。