溶胶-凝胶法固定脂肪酶的方法研究

采用溶胶-凝胶技术,以正硅酸乙酯为前驱物,制备了S iO2微粒,以3-氨基丙基三乙氧基硅烷作偶联剂对S iO2微粒进行表面改性,制备了一种功能化载体3-氨基丙基硅胶。以甲醛为偶联剂,将脂肪酶固定于3-氨基丙基硅胶上。用红外光谱对产物结构进行表征,同时研究了固定化酶的性质。结果表明,氨基化硅胶交联固定化脂肪酶具有可行性,固定化酶的最适反应温度在30℃附近,且在碱性范围内其稳定性比自然酶高;当pH=7.5,其它条件相同时,自然酶的活力大于固定化酶的活力。     

Preparation and properties of organosoluble polyimide/silica hybrid materials by sol–gel process

Organosoluble polyimide/silica hybrid materials were prepared using the sol–gel process. The organosoluble polyimide was based on pyromellitic anhydride (PMDA) and 4,4′‐diamino‐3,3′‐dimethyldiphenylmethane (MMDA). The silica particle size in the hybrid is increased from 100–200 nm for the hybrid containing 5 wt % silica to 1–2 µm for the hybrid containing 20 wt % silica. The strength and the toughness of the hybrids are improved simultaneously when the silica content is below 10 wt %. As the silica content is increased, the glass transition temperature (T_g) of the hybrids is increased slightly. The thermal stability of the hybrids is improved obviously and their coefficients of thermal expansion are reduced. The hybrids are soluble in strong polar aprotic organic solvents when the silica content is below 5 wt %. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2977–2984, 1999     

A polyamide-silica composite prepared by the sol-gel process

Summary A new kind of organic-inorganic hybrid composite was prepared by means of the sol-gel process. The polymer employed was a mixed-isomer aromatic polyamide having good solubility and thermal stability. The silica constituting the inorganic phase was produced by the hydrolysis and condensation of tetramethoxysilane. The bonding between the phases involved aminophenyl-trimethoxysilane, in which the amino group can react with the phthaloyl chloride end-capped polymer, and the methoxysilane groups undergo hydrolysis. The composition of these composites was varied by changing the linear polymer chain length and relative amount of tetramethoxysilane. The gelation time was found to range from a few minutes to several days. Thermogravimetric analyses showed that decomposition starts at approximately 450 °C. Thin films cast from materials having a relatively high silica content were opaque and rigid, but those with low silica content were flexible and transparent.     

溶胶-凝胶法聚丙烯酸丁酯/二氧化硅杂化材料弹性体的制备与表征

用丙烯酸丁酯与少量功能单体共聚,合成了分子链侧基带羟基的聚丙烯酸丁酯(PBA)乳液,然后与硅溶胶混合,用溶胶-凝胶法制备了PBA/SiO2杂化材料弹性体;研究了SiO2含量对杂化材料弹性体力学性能及透光率的影响,并用扫描电子显微镜、傅里叶变换红外光谱、差示扫描量热分析和动态力学性能分析对杂化材料弹性体的结构进行了表征。结果表明,PBA/SiO2杂化材料热压后成为一种力学性能优良的具有一定透光率的弹性体。随着SiO2含量的增加,杂化材料弹性体的力学性能提高,透光率和SiO2粒子的粒径增加,PBA基体的玻璃化转变温度和损耗因子下降;PBA共聚物分子链侧基所带羟基与SiO2粒子表面的硅醇基发生了缩合脱水反应,形成了Si—O—C共价键,使PBA基体与SiO2粒子构成的界面结合紧密,从而赋予杂化材料弹性体以优良的性能。     

耐水硅胶材料制备工艺条件优化实验研究

运用正交实验设计及方差分析方法,以耐水硅胶材料的比表面积和孔容为考察指标,研究了在硅胶制备过程中硫酸铝溶液质量分数、原料硫酸与硫酸铝物质的量比等因素对实验结果影响的显著性。结果表明,硫酸铝溶液质量分数及原料硫酸与硫酸铝物质的量比对实验结果影响最为显著。最优工艺参数：硫酸铝溶液质量分数为6%,原料硫酸与硫酸铝物质的量比为2∶1,酸泡过程硫酸与硫酸铝物质的量比为6∶1,碱泡过程中稀氨水质量分数为0.1%,老化时间为1.5 h。在最优工艺条件下,可得到比表面积不低于300  m²/g、孔容不低于0.7 mL/g的具有良好耐水性的吸附分离材料。     

In situ polyurethane/silica composite formation via a sol‐gel process

Polyurethane acrylate anionomer (PUAA)/silica composite gels were prepared by the sol‐gel reaction of tetraethoxysilane (TEOS) and methacryloxypropyl trimethoxysilane (MPTS) incorporated to PUAA gels by using a swelling method. The formation and structure of composites were confirmed by FTIR, X‐ray diffraction, and SEM. As a result, we found that silica components in composites are located within the ionic domains of their gels and interacted with PUAA via hydrogen bonding. This drastically enhanced the mechanical properties of the composites. Mechanical properties are also improved by MPTS, because MPTS improves the dispersibility and adhesion of silica components in PUAA/silica composite gels. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2327–2334, 2002     

sol-gel法制备微孔SiO2分离膜的研究进展

微孔SiO2分离膜在气体分离、催化、膜反应器等领域有着巨大的应用潜力。本文首先简要介绍了获得微孔的两种途径，然后重点对sol—gel法制备微孔SiO2分离膜的研究进展进行综述。     

Preparation and properties of rigid‐rod polyimide/silica hybrid materials by sol–gel process

Polyimide (PI) materials with a low coefficient of thermal expansion (CTE) while still retaining high strength and toughness are desirable in various applications. In this study a sol–gel process was used to incorporate silica into homopolyimides and copolyimides with highly rigid structures in an attempt to pursue this aim. A number of highly rigid monomers were used, including pyromellitic dianhydride (PMDA), p‐phenylene diamine (PPA), m‐phenylene diamine (MPA), benzidine, 2,4‐diaminotoluene, and o‐toluidine. No homopolyimide flexible films were obtained. However, it was possible to obtain flexible films from the copolyimides. Therefore, a copolyimide based on PPA, MPA, and PMDA (PPA/MPA = 2/1 mol) was then chosen as the matrix to prepare the PI/silica hybrids. Flexible films were obtained when the silica content was below 40 wt %. The hybrid films possessed low in‐plane CTEs ranging from 14.9 to 31.1 ppm with the decrease of the silica content. The copolyimide film was strengthened and toughened with the introduction of an appropriate amount of silica. The thermal stability and the Young's modulus of the hybrid films increased with the increase of the silica content. The silica particle size was assessed by scanning electron microscopy and was about 100 nm for the hybrids containing 10 and 20 wt % silica and 200–500 nm for the hybrids containing 30 and 40 wt % silica. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 794–800, 2001     

硅胶的发展现状及应用

硅胶的化学性质稳定、吸附性能高、热稳定性好、较高的机械强度,是一种高活性多孔材料。硅胶生产方法很多,以硅酸钠和无机酸为原料的溶胶-凝胶法应用最为广泛。硅胶改性包括硅胶扩孔和硅胶负载,改性后的硅胶,性能优良,应用更为广泛。硅胶负载金属镍是一种很好的脱除油品中氮化物的吸附剂,金属负载量、吸附温度、吸附时间不同,硅胶吸附脱氮的效果也不同。目前,硅胶已经广泛应用到各行各业,硅胶在石油化工、医药、食品、油墨、农业的应用发展迅速。     

溶胶-凝胶法制备硅酸铝耐火纤维

本文以正硅酸乙酯(TEOS)、异丙醇铝(AIP)、硝酸铝(AN)等为原料，用溶胶-凝胶(so1-ge1)法制备硅酸铝耐火纤维．     

Synthesis and characterization of nanocomposite of polyimide–silica hybrid from nonaqueous sol–gel process

Polyimide–silica (PI–SiO₂) hybrids with a nanostructure was obtained using the nonaqueous sol–gel process by polycondensation of phenyltriethoxysilane in a polyamic acid solution. Self‐catalyzed hydrolysis of phenyl‐substituted akoxysilane and modification on the polyimide structure are applied and result in highly compatible PI–SiO₂ hybrids. Transparent PI–SiO₂ with a high silica content of about 45% was thus obtained. The prepared PI–SiO₂ films were characterized by infrared spectrometry, ²⁹Si‐NMR, thermogravimetric analysis, differential scanning calorimetry, and scanning electron microscopy. These characterizations showed the silica influence on the properties of the hybrid. The thermal expansion coefficient of the PI–SiO₂ and the temperature correlation were also established for probing the potential for application. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1609–1618, 2000     

湿化学法制备超细二氧化硅粉体材料

随着超细二氧化硅应用领域的不断扩大，对其制备技术提出了新的要求。综述了目前制备超细二氧化硅粉体常用的两种湿化学法，即化学沉淀法和溶胶-凝胶法。并从反应机理、工艺控制、影响因素、存在问题等方面对两种方法进行了比较和评述，从而为综合改善制备的工艺条件提供了依据。     

Transparent photo‐curable co‐polyacrylate/silica nanocomposites prepared by sol‐gel process

This work prepared the highly transparent photo‐curable co‐polyacrylate/silica nanocomposites by using sol‐gel process. The FTIR and ¹³C NMR analyses indicated that during the sol‐gel process, the hybrid precursors transform into composites containing nanometer‐scale silica particles and crosslinked esters/anhydrides. Transmission electron microscopy (TEM) revealed that the silica particles within the average size of 11.5 nm uniformly distributed in the nanocomposite specimen containing about 10 wt % of Si. The nanocomposite specimens exhibited satisfactory thermal stability that they had 5% weight loss decomposition temperatures higher than 150°C and coefficient of thermal expansion (CTE) less than 35 ppm/°C. Analysis via derivative thermogravimetry (DTG) indicated that the crosslinked esters/anhydrides might influence the thermal stability of nanocomposite samples. The UV‐visible spectroscopy indicated that the nanocomposite resins possess transmittance higher than 80% in visible light region. Permeability test revealed a higher moisture permeation resistance for nanocomposite samples, which indicated that the implantation of nano‐scale silica particles in polymer matrix forms effective barrier to moisture penetration. Adhesion test of nanocomposite samples on glass substrate showed at least twofold improvement of adhesion strength compared with oligomer. This evidenced that the silica and the hydrophilic segments in nanocomposite resins might form interchains hydrogen bonds with the ? OH groups on the surface of glass so the substantial enhancement of adhesion strength could be achieved. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

微通道内双重孔结构SiO2微球的制备

利用微流控技术制备双重孔结构SiO₂微球具有微观结构和宏观形貌可控的优点。在同轴环管微通道中,通过pH和温度变化引发快速凝胶过程制备得到了具有双重孔结构的SiO₂微球,考察了有机相溶剂性质、有机相流速以及凝胶温度等因素对微球宏观形貌以及微观结构的影响规律。实验结果表明,制备得到的SiO₂微球粒径在300～600 μm可调,比表面积可以达到1000 m²·g^-1,介孔孔径在4～10 nm之间,大孔孔径在400～1500 nm之间。实验发现有机相流速的增大会导致微球粒径的减小,提高三辛胺对盐酸的萃取速率,加快二氧化硅溶胶粒子的凝胶过程,更易生成松散的网状大孔结构。较高的凝胶温度会增大SiO₂微球介孔的孔容和孔径。     

溶胶-凝胶法制备氧化硅-氧化铝体系凝胶及合成过程研究进展

氧化硅-氧化铝（SiO₂-Al₂O₃）体系凝胶不仅应用广泛,而且其制备及反应机理还可借鉴到碱激发胶凝材料等领域。通过对溶胶-凝胶法合成氧化硅-氧化铝体系凝胶的制备过程及影响因素和影响规律、凝胶的性质和结构表征及合成机理研究进展进行综述,提出目前仍缺乏有关碱（土）金属离子对凝胶结构性能的影响研究以及硅铝含量变化的定量描述数据,建议拓宽研究范畴,结合核磁共振等检测方法,得出该体系结构性能变化准确数据,为氧化硅-氧化铝体系凝胶的设计和应用夯实基础。     

A comparison of nitrogen adsorption and thermogravimetric methods in the assessment of the pore size distribution of mesoporous silica gels

The pore dimensions are determined by using adsorption and thermogravimetry methods for unmodified silica gel Si-100 and silanized silica gel Lichrosorb RP-18. Thermal desorption measurements for various liquids were performed under quasi-isothermal conditions. Methanol, acetone, benzene and n-hexane were used as a wetting liquids. Pore size distributions and total pore volumes derived from thermal desorption compare reasonably well with results obtained from the analysis of adsorption isotherms of nitrogen. For different types of adsorbates the effects connected with the presence of the surface liquid film are discussed. The presence of long alkyl chains on the silica surface strongly influences the pore diameter calculated from thermogravimetric data.     

硅胶催化合成3,6-二溴咔唑

以咔唑、N-溴代丁二酰亚胺(NBS)为原料,硅胶为催化剂,合成3,6-二溴咔唑,考察了反应时间、原料配比、溶剂用量和催化剂用量对反应的影响。正交实验表明,较佳工艺条件为:咔唑、NBS的摩尔比为1∶2,二氯甲烷50 mL,硅胶17 g时,室温下反应12 h,收率达89.25%,熔点为213.5℃。产物结构经TLC、IR进行表征。     

Surface functionalized colloidal silica particles from an inverse microemulsion sol gel process

Colloidal silica particles are prepared via a sol gel technique carried out in an inverse microemulsion of water in a toluene solution of tetraethoxysilane (TEOS), stabilized by either an anionic surfactant AOT or isopropanol. Functionalized material was obtained using a functional coupling agent (RO)₃Si(CH₂)₃ X, X being a functional group such as methacryloyl, thiol, vinyl, amino group, or a chlorine atom. Functionalization can be carried out either directly via the direct copolycondensation of TEOS and the coupling agent, or in a two-step process involving a core-shell polycondensation of the coupling agent onto preformed silica particles. Kinetic studies of the copolycondensation are carried out using either²⁹Si NMR analysis or liquid chromatography. They show that the consumption of TEOS is more rapid than that of the coupling agent. The materials are characterized both chemically (elemental analysis, FTIR,¹³C and²⁹Si NMR CPMAS analysis), and by their particle size. The silica functionalized with a polymerizable methacryloyl group is encapsulated by a polymer layer in an inverse emulsion polymerization of acrylic acid. After inversion of the emulsion in water, the resulting material is covered with a layer of hydrophobic polymer in a conventional emulsion polymerization.     

硅胶及其混合吸附剂——水吸附工质对性能测试

测试了硅胶-水吸附制冷工质对的等量吸附线,且利用各类吸附方程对实验测量数据进行拟合以用于硅胶-水冷水机组的整体系统的数值模拟。实验还通过在纯硅胶颗粒中添加黏结剂或膨胀石墨形成混合吸附剂来提高传热性能。研究表明混合吸附剂（黏结剂的含量为1.1％）在解吸过程中前5min的解吸量相对于纯硅胶颗粒吸附剂提高了13.8％;解吸15min时,混合吸附剂的解吸量相对于纯吸附剂仅提高2.5％。表明混合吸附剂有利于缩短吸附循环周期。在添加剂质量分数相同的情况下,利用膨胀石墨作添加剂形成的混合吸附剂与通过浸泡于黏结剂溶液中形成的混合吸附剂的吸附性能相同,但有其各自的优缺点。