合成三氯甲硅烷中多氯硅烷与甲基氯硅烷的形态分析

合成三氯甲硅烷中常含有多氯硅烷类和甲基氯硅烷类物质。目前对它们的研究仅限于理论方面,而实验研究较少。本文采用气相色谱质谱联用技术对合成的三氯甲硅烷中含有的多氯硅烷进行了解析,确认主要成分是六氯乙硅烷,其次是六氯乙硅氧烷和五氯乙硅烷;通过间接测试的方法实现了甲基氯硅烷与三氯甲硅烷、四氯化硅在HP-5ms色谱柱上的完全分离,并确认甲基氯硅烷类主要是甲基二氯硅烷、二甲基氯硅烷、甲基三氯硅烷。     

Ⅳ.硅烷与烯腈结构对硅氢加成反应的影响

在三组分催化剂——三正丁胺、四甲基乙二胺、氯化亚铜作用下,进行不同硅烷(三氯硅烷、苯基二氯硅烷、甲基二氯硅烷、二苯基氯硅烷、甲基苯基氯硅烷、二乙基氯硅烷、三乙基硅烷)与丙烯腈的加成反应。在相同的反应条件下,对于七种硅烷的活性作定量的比较,发现加成产率百分数与相应的硅烷基团的诱导效应指数间形成一正 S 型曲线。改变烯腈结构(α-氰基丙烯酸乙酯、丙烯腈、α-甲基丙烯腈、α-乙基丙烯腈、丁烯腈),研究其在三氯硅烷加成反应中的影响,同样也得到产率百分数的正 S 型曲线。基于与 Grignard 试剂的反应和碱性水解作用,确定加成产物的结构。实验表明,硅原子系加在烯腈的β-碳上(β-加成)。根据结构活性关系的 S 型曲线讨论加成反应的机理。     

倍半硅氧烷合成进展

对以苯基三氯硅烷、苯基三烷氧基硅烷、甲基三氯硅烷、甲基三烷氧基硅烷、甲基三乙酸基硅烷分别为原料采用碱催化平衡水解三步法合成可溶性高分子量聚倍半硅氧烷及其共聚物进行了综述,并对以苯基三氯硅烷为原料采取一步法合成热塑性聚苯基倍半硅氧烷予以介绍,总结了以不同有机基为原料采用碱催化平衡法合成不溶性立方体聚倍半硅氧烷的研究结果,最后对卤盐催化非水解sol-gel法制备有机倍半硅氧烷凝胶作了阐述,以期对合成不同结构的聚倍半硅氧烷提供帮助。     

含氯硅烷/聚硅氧烷改性环氧树脂

含氯硅烷/聚硅氧烷改性环氧树脂;环氧树脂;α;ω-二氯聚二甲基硅氧烷;一氯三甲基硅烷;二氯二甲基硅烷;电子封装     

梯形苯基/甲基聚倍半硅氧烷树脂的合成及热稳定性研究

以苯基三氯硅烷和甲基三氯硅烷为主要原料,以不同摩尔比(1:1,2:1,3:1)合成了三种梯形聚苯基/聚甲基倍半硅氧烷树脂(1～3),其结构经UV和IR表征.热重分析发现,1～3的热分解温度分别为470 ℃,517 ℃和540 ℃,说明随着苯基三氯硅烷与甲基三氯硅烷摩尔比增大,热稳定性增加.用量子化学方法计算发现苯基硅氧烷的C-Si键长比甲基硅氧烷C-Si键短,且更牢固.     

一种高折光率发光二极管封装硅树脂的研制

将甲基苯基二氯硅烷(MePhSiCl₂)与二甲基二氯硅烷(Me₂SiCl₂)、 甲基乙烯基二氯硅烷(MeViSiCl₂)和苯基三氯硅烷(PhSiCl₃)等共水解后, 在KOH催化下共缩聚, 以三甲基氯硅烷(Me₃SiCl)为封端剂, 制备了含有甲基苯基硅氧链节的甲基苯基乙烯基硅树脂, 并利用FTIR, ¹H NMR和热重分析(TGA)对产物进行了表征. 将所得甲基苯基乙烯基硅树脂与甲基苯基含氢硅油按一定配比, 在铂络合物催化下硫化成型, 制成发光二极管(LED)封装A/B胶, 用于LED封装. 所得LED封装硅树脂固化后在可见光范围内具有非常高的透光率. 对LED的封装结构进行优化, 获得的LED具有高光效、 高光通量、 窄显色指数和高色温一致性等优点, 可满足功率型LED封装要求.     

外光源大屏幕电视机的油膜合成——1,3,5-三甲基-1,3,5-三苯基-1,5-二邻苯基苯氧基-三硅氧烷的合成

电视油膜是外光源大屏幕电视机的成像介质,是化学合成材料。本文仅报导其油膜1,3,5-三甲基-1,3,5-三苯基-1,5-二邻苯基苯氧基-三硅氧烷(下称化合物I)的合成。我们参考了 James G.Murray等报导的资料,采用以甲基苯基二氯硅烷为主要原料,首先制得甲基苯基邻苯基苯氧基氯硅烷,再制备成其硅醇,最后与甲基苯基二氯硅烷进行缩合反应,经减压蒸馏,收集235     

3—氯丙基三甲氧基硅烷的合成

采用氯铂酸／异丙醇和三苯基膦／环己酮为催化剂，在室温下能够使三氯硅烷与３－氯丙烯迅速发生硅氢加成反应，高产率地生成３－氯丙基三氯硅烷，继而将３－氯丙基三氯硅烷与无水甲醇同时中到沸腾的石油醚中进行醇解，合成了３－氯丙基三甲氧基硅烷。     

苯基化纳米MCM-41材料的制备与表征

以苯基三甲氧基硅烷为偶联剂对纳米MCM-41分子筛进行了有机改性,制备了苯基改性的纳米MCM-41分子筛MCM-41(m)。利用元素分析、粉末XRD、傅里叶变换红外光谱、氮气吸附-解吸附、扫描电镜和差热-热重分析对制备产物进行了表征。粉末XRD结果表明,改性过程中,分子筛骨架未被破坏,并且所制备MCM-41(m)分子筛结晶度依然很高;傅里叶变换红外光谱表明苯官能团已经成功地接枝到了分子筛的孔道表面,且所得产物的骨架依然完好;低温氮气吸附-解吸附分析结果表明,MCM-41(m)分子筛孔道具有高度有序性,改性的纳米MCM-41分子筛孔道内的硅羟基与苯基三甲氧基硅烷发生了硅烷化反应,苯基成功地接枝到了分子筛的孔道表面。扫描电镜结果表明, 制得的苯基改性纳米MCM-41平均尺寸为110 nm。差热-热重分析结果说明了所制备的苯基化的纳米MCM-41样品具有良好的热稳定性,骨架稳定温度为823 ℃。苯基化的纳米MCM-41材料具有作为催化剂材料的潜在应用前景。     

3－氯丙基三甲氧基硅烷的合成

采用氯铂酸／异丙醇和三苯基膦／环己酮为催化剂，在室温下能够使三氯硅烷与３－氯丙烯迅速发生硅氢加成反应，高产率地生成３－氯丙基三氯硅烷，继而将３－氯丙基三氯硅烷与无水甲醇同时滴加到沸腾的石油醚中进行醇解，合成了３－氯丙基三甲氧基硅烷     

Size separation and size determination of liposomes

We developed a method for separating liposomes by size and determining their average diameters. Liposomes with different average diameters were separated on a monolithic silica capillary column, and the size of the liposomes corresponding to each peak was determined online with a dynamic light scattering detector coupled to the capillary liquid chromatography system. The calculated diameters for the separated liposomes were similar to the diameter values measured in batch mode. We demonstrate that this combination of a monolithic capillary column and light scattering detection could be used for size separation of liposomes and could provide more details about average diameters than batch-mode analysis.     

用毛细管色谱法分析14种拟除虫菊酯立体异构体

 用石英毛细管柱分离了14种拟菊酯的立体异构体。柱1用QF-1固定液10m×0.53mm×1.0μm膜厚，柱温在180℃～260℃之间，可完全分离右旋丙炔菊酯等10种拟菊酯的立体异构体。往2为HP-525m×0.53mm×1.0μm膜厚，用合适的住温可分离百治菊酯等4种拟菊酯的异构体。     

Ionic liquids as stationary phase solvents for methylated cyclodextrins in gas chromatography

Summary Room temperature ionic liquids (RTIL) are molten salts with melting points well below room temperature. 1-butyl-3-methylimidazolium chloride is a typical example of such RTIL. It was used as a solvent to dissolve permethylated-β-cyclodextrin (BPM) and dimethylated-?cyclodextrin (BDM) to prepare stationary phases for capillary columns in gas chromatography for chiral separation. The RTIL containing columns were compared to commercial columns containing the same chiral selectors. A set of 64 chiral compounds separated by the commercial BPM column was tested on the RTIL BPM column. Only 21 were enantioresolved. Similarly, a set of 80 compounds separated by the commercial BDM column was passed on the RTIL BDM column with only 16 positive separations. It is proposed that the imidazolium ion pair could make an inclusion complex with the cyclodextrin cavity, blocking it for chiral recognition. All the chiral compounds recognized by the RTIL columns had their asymmetric carbon that was part of a ring structure. The retention factors of the derivatized solutes were lower on the RTIL columns than those obtained on the commercial equivalent column. The peak efficiencies obtained with the RTIL capillary were significantly higher than that obtained with the commercial column. These observations may contribute to the knowledge of the mechanism of cyclodextrin-based GC enantioselective separations.     

气相色谱法分析高纯异丁烯中的微量烃类杂质

 采用HP Al2O3/S PLOT(50 m×0.32 mm i.d.×8 μ m) 毛细管色谱柱对高纯异丁烯中的微量烃类杂质进行了气相色谱方法研究。结果表明,该色谱柱能很好地分离异丁烯中的C1~C4烃类杂质;采用液相进样阀液态直接进样，保证样品不失真,所测定的结果有良好的准确度和精密度。     

气相法分析化妆品中的防腐剂

 采用大口径中极性毛细管柱HP 170 1(15m× 0 5 3mmi d × 1 0 μm)对苯甲醇、对羟基苯甲酸甲酯、对羟基苯甲酸乙酯、对羟基苯甲酸丙酯和对羟基苯甲酸丁酯等化妆品中常用的 5种防腐剂进行了气相分析方法研究。结果表明 ,该毛细管柱能够很好地分离这 5种化合物 ,抗干扰性良好 ,其检出限分别是 13ng ,70ng ,70ng ,10 0ng和 10 0ng ,线性范围为 5 0ng～ 5 0 0ng。     

The synthesis of chloropropyl-functionalized silica hybrid monolithic column with modification of N,N-dimethyl-N-dodecylamine for capillary electrochromatography separation

A chloropropyl-functionalized silica (CP-silica) hybrid monolithic column was synthesized within the confines of a capillary via the sol–gel process using tetramethoxysilane (TMOS) and (3-chloropropyl)-trimethoxysilane (CPTMS) as the precursors. The resulting CP-silica hybrid monolith inside the capillary showed homogeneous macroporous morphology and was well attached to the inner wall of the capillary. The obtained CP-silica hybrid monolithic capillary column demonstrated the inherent hydrophobic property and could be applied as a reversed-phase stationary phase in CEC directly. Due to the great chemical reactivity of the incorporated chloro groups on the hybrid silica monolithic matrix, the chloropropyl moieties on the surface of the hybrid silica monolith matrix could be conveniently further modified by a tertiary amine of N,N-dimethyl-N-dodecylamine (DMDA) via the nucleophilic substitution reaction at 70 °C to introduce a dodecyl groups (C12) onto the CP-silica hybrid monolithic matrix. The resulting C12-silica hybrid monolithic column not only demonstrated the significantly enhanced hydrophobic property in the separation of alkylbenzenes in reversed-phase capillary electrochromatography (RP-CEC), but also the strong electroosmotic flow (EOF) in a wide pH range. Five alkylbenzenes could be baseline separated in 3 min with column efficiency ranging from 189 700 to 221 000 N/m with a 70% ACN running buffer in CEC.     

甲基氯硅烷初产品的组成分析

以气相色谱和色谱-质谱联用技术分析了甲基氯硅烷初产品的组成,对于其中的2-甲基-2-丁烯与甲基二氯硅烷的色谱重叠峰,采用醇解反应处理,并以样品中不会醇解的四甲基硅烷做参照来计算其含量。     

Carboxymethylchitosan covalently modified capillary column for open tubular capillary electrochromatography of basic proteins and opium alkaloids

A novel open tubular (OT) column covalently modified with hydrophilic polysaccharide, carboxymethylchitosan (CMC) as stationary phase has been developed, and employed for the separations of basic proteins and opium alkaloids by capillary electrochromatography (CEC). With the procedures including the silanization of 3-aminopropyltrimethoxysilane (APTS) and the combination of glutaraldehyde with amino-silylated silica surface and CMC, CMC was covalently bonded on the capillary inner wall and exhibited a remarkable tolerance and chemical stability against 0.1 mol/L HCl, 0.1 mol/L NaOH or some organic solvents. By varying the pH values of running buffer, a cathodic or anodic EOF could be gained in CMC modified column. With anodic EOF mode (pH<4.3), favorable separations of basic proteins (trypsin, ribonuclease A, lysozyme and cytochrome C) were successfully achieved with high column efficiencies ranging from 97,000 to 182,000 plates/m, and the undesired adsorptions of basic proteins on the inter-wall of capillary could be avoided. Good repeatability was gained with RSD of the migration time less than 1.3% for run-to-run (n=5) and less than 3.2% for day-to-day (n=3), RSD of peak area was less than 5.6% for run-to-run (n=5) and less than 8.8% for day-to-day (n=3). With cathodic EOF mode (pH>4.3), four opium alkaloids were also baseline separated in phosphate buffer (50 mmol/L, pH 6.0) with column efficiencies ranging from 92,000 to 132,000 plates/m. CMC-bonded OT capillary column might be used as an alternative medium for the further analysis of basic proteins and alkaline analytes.     

牛血清蛋白对手性物质的毛细管电泳拆分

采用聚氧乙烯涂层毛细管柱，以牛血清蛋白(BSA)为手性添加剂，运用毛细管电泳电导检测对手性药物沙丁胺醇和多沙唑嗪以及DL-组氨酸、色氨酸、苏氨酸进行拆分。考察了涂层柱的稳定性和重现性。对影响手性分离的主要因素：缓冲溶液的浓度和酸度、BSA的浓度、有机溶剂的种类和浓度以及分离电压进行了系统的研究。结果表明：在选择的最佳实验条件下，各对映异构体在22min内得到基线分离。     

Study on open tubular capillary affinity liquid chromatography

A novel mode of affinity chromatography (AC) based on an open tubular capillary column (OTAC) is demonstrated. The OTAC column is prepared by immobilizing Cibacron blue F3GA onto the inner surface of a 50-microm-i.d. capillary column. The AC experiment is performed on a capillary electrophoresis instrument by using its pressure system as the driving force. Bovine serum albumin and lysozyme (Lys) are successfully separated with stepwise gradient elution. The relative standard deviation (RSD) for the elution time of the retained Lys is 0.08%, and good repeatability of its peak area and peak height with an RSD value lower than 2.12% for 10 consecutive runs is observed. The loading capacity and detection limit for the retained Lys are approximately 36 ng and 8.6 ng, respectively. It is also found that the amount of protein adsorbed is unaffected by the flow rate of the loading buffer, and OTAC can be used for the fast determination of biopolymers. Some of the advantages of OTAC over conventional modes of open tubular capillary liquid chromatography are that the detection sensitivity and loading capacity of a sample can be greatly improved, because the relatively large inner diameter of the capillary can be adopted and the whole capillary column can be used to adsorb the solute in OTAC.