甲基丙烯酸3-三甲氧基硅丙酯/苯乙烯细乳液共聚合过程中的水解及缩合反应

研究了甲基丙烯酸3-三甲氧基硅丙酯(MPS)和苯乙烯(St)细乳液聚合过程中的水解及缩合反应.用气相色谱仪测定聚合过程中水解产物——甲醇的含量来研究MPS的水解度.MPS分子主要在细乳液液滴与水的界面以及乳胶粒与水的界面上发生水解反应.MPS和St比例、介质pH值、乳化剂用量、引发剂类型和用量都会影响MPS的水解程度.缩合产物用29Si固态核磁共振表征,中性条件下,缩合反应受到抑制,在高MPS/St比例的体系中也只生成少量缩合产物.酸性和碱性条件下,缩合产物量均增加,但碱性条件下,体系中仍有一定数量未缩合的硅氧烷存在,这与细乳液聚合独特的液滴成核机理及聚合过程中较少液滴间物质交换有关.     

由硅溶胶生长单分散颗粒的研究

针对现行单分散二氧化硅颗粒制备方法的粒径预见性差、步骤繁琐、收率低等问题，研究了一种用硅溶胶作为种子，在氨、水和乙醇的混合溶液中通过水解正硅酸乙酯（ＴＥＯＳ）生长出单分散颗粒的简便方法。该方法仅在初始的悬浮液中滴加ＴＥＯＳ即可使种子正常生长，无须补充氨水以修正体系浓度的变化。最终的分散相浓度可达１０％（质量分数）。可选择生长的粒径范围在１微米以内并可精确控制。所得颗粒粒径分布偏差于Ｓｔｏｂｅｒ方法     

Fabrication of spherical colloidal crystals using electrospray

We demonstrated the use of electrohydrodynamic atomization to prepare uniform-sized emulsion droplets in which equal spheres of silica or polystyrene were dispersed. The size of the emulsion droplets was easily controlled by the electric field strength and the flow rate, independently of the diameter of the nozzles. During the evaporation of solvent in the droplets, spherical colloidal crystals were formed by self-assembly of the monodisperse colloidal spheres. The diameter of the spherical colloidal crystals was in the range of 10-40 microm. Depending on the stability of colloidal particles, the morphology of the self-assembled structure was varied. In particular, silica spheres in ethanol droplets were self-assembled into compactly packed silica colloidal crystals in spherical shapes, whereas polystyrene latex spheres in toluene droplets self-assembled into spherical colloidal crystal shells with hollow cores. The silica colloidal assemblies reflected diffraction colors according to the three-dimensionally ordered arrangement of silica spheres.     

Formation of silica nanoparticles in microemulsions

Silica nanoparticles for controlled release applications have been produced by the reaction of tetramethylorthosilicate (TMOS) inside the water droplets of a water-in-oil microemulsion, under both acidic (pH 1.05) and basic (pH 10.85) conditions. In-situ FTIR measurements show that the addition of TMOS to the microemulsion results in the formation of silica as TMOS, preferentially located in the oil phase, diffuses into the water droplets. Once in the hydrophilic domain, hydrolysis occurs rapidly as a result of the high local concentration of water. Varying the pH of the water droplets from 1.05 to 10.85, however, considerably slows the hydrolysis reaction of TMOS. The formation of a dense silica network occurs rapidly under basic conditions, with IR indicating the slower formation of more disordered silica in acid. SAXS analysis of the evolving particles shows that approximately 11 nm spheres are formed under basic conditions; these are stabilized by a water/surfactant layer on the particle surface during formation. Under acidic conditions, highly uniform approximately 5 nm spheres are formed, which appear to be retained within the water droplets (approximately 6 nm diameter) and form an ordered micelle nanoparticle structure that exhibits sufficient longer-range order to generate a peak in the scattering at q approximately equal to 0.05 A-1. Nitrogen adsorption analysis reveals that high surface area (510 m2/g) particles with an average pore size of 1 nm are formed at pH 1.05. In contrast, base synthesis results in low surface area particles with negligible internal porosity.     

Fabrication of silica nanoparticles and hollow spheres using ionic liquid microemulsion droplets as templates

Silica products with two different morphologies were synthesized using nonaqueous ionic liquid microemulsion droplets as templates. The morphologies of the obtained products were characterized by both transmission electron microscopy (TEM) and scanning electron microscopy (SEM). By adjusting the reaction conditions, ellipsoidal nanoparticles were formed under acidic conditions, while hollow silica spheres were obtained under alkaline conditions. It is demonstrated that the size distribution of hollow silica spheres was narrower than that of the ellipsoidal nanoparticles. The various vibration modes of different functional groups in the silica materials were revealed by Fourier transform infrared (FTIR) spectroscopy. The two samples were both shown to be amorphous, not crystalline by X-ray diffraction (XRD). A simple diagram of the formation process including the hydrolysis and condensation reactions is given. Furthermore, a probable mechanism for the formation of silica materials under acidic or alkaline conditions is presented, which may be helpful for better understanding the different silica materials obtained under different conditions.     

Synthesis of Microporous Silica Spheres

Spherical microporous silica powders with a narrow size distribution have been prepared by a precipitation technique involving the hydrolysis reaction of a silicon alkoxide in ethanol. The formation of the important microporosity has been investigated following two templating methods: the co-hydrolysis and condensation of two alkoxides, one of which presents porogen function, and the adsorption of an organic compound (glycerol) as the porogen. In both processes, the organic porogen is removed by a simple calcination. In the first method, the addition of more than 20 mol% of the porogen alkoxide, necessary for generating enough microporosity, disturbs completely the condensation process resulting in microporous, nonuniform silica particles of large size distribution. The best result has been obtained with the glycerol method where submicrometer-sized silica spheres with a very narrow size distribution and about 40 vol% porosity have been synthesized. The presence of glycerol during the synthesis considerably affects the precipitation mechanism, resulting in a larger mean particle size. The use of an aggregative growth model has successfully been employed to explain the effect of the porogen during particle formation. The precipitation mechanism of silica involves the aggregation between particles of similar size until a critical size is reached, resulting in a uniform particle size distribution. In the presence of glycerol, it has been shown that a second aggregative growth between still-nucleating primary particles and large particles occurred with increasing reaction time. This second aggregative growth appears at an intermediate stage of the precipitation process and is due to both the precipitation of smaller primary particles and the destabilization of the colloidal stability of the system. This explains why the final particle size reached in this system is larger compared to silica particles synthesized without glycerol and shows how glycerol is incorporated in the silica particles. The synthesis of silica microporous spheres of narrow size distribution, by varying particle size and porosity, should yield a wide range of aqueous silica slurries for particular chemical mechanical polishing applications. Copyright 2000 Academic Press.     

Ionic transport across tailored nanoporous anodic alumina membranes

Monodispersed silica particles with bimodal size distribution were successfully prepared through adding an ethanol (EtOH) solution containing tetraethylorthosilicate (TEOS) dropwise into an ammonia EtOH solution at a constant low rate. The effects of the reaction parameters such as ammonia/ethanol ratio, feeding rate of TEOS solution, reaction temperature, and time on the size and size distribution of the as-obtained particles were investigated. Based on these phenomena, a modified LaMer model of nucleation and growth mechanism was proposed to reasonably explain the formation of the as-obtained silica particles with bimodal size distribution. The as-prepared monodispersed silica particles with bimodal size distribution can be directly fabricated into binary colloidal crystals with small particles surrounding large particles by evaporation-induced cooperative self-assembly. This suggests that the method reported here provides a straightforward and effective route to the in situ fabrication of novel binary colloidal crystals and their replicated patterns in one reaction system.     

Preparation of mesoporous submicrometer silica capsules via an interfacial sol-gel process in inverse miniemulsion

Mesoporous silica capsules with submicrometer sizes were successfully prepared via the interfacial hydrolysis and condensation reactions of tetraethoxysilane (TEOS) in inverse miniemulsion by using hydrophilic liquid droplets as template. The inverse miniemulsions containing pH-controlled hydrophilic droplets were first prepared via sonication by using poly(ethylene-co-butylene)-b-poly(ethylene oxide) (P(E/B)-PEO) or SPAN 80 as surfactant. TEOS was directly introduced to the continuous phase of an inverse miniemulsion. The silica shell was formed by the deposition of silica on the surface of droplets. The formation of capsule morphology was confirmed by transmission electron microscopy (TEM) and field emission scanning electron microscopy (FESEM). The mesoporous structure was verified by nitrogen sorption measurements. The specific surface area could be tuned by the variation of the amount of cetyltrimethylammonium bromide (CTAB) and TEOS, and the pore size by the amount of CTAB. The influences of synthetic parameters on the particle size and morphology were investigated in terms of the amount of CTAB, pH value in the droplets, TEOS amount, surfactant amount, and type of solvent with low polarity. A formation mechanism of silica capsules was proposed.     

Synthesis of polymer–inorganic patchy microcapsules with tunable patches

We introduce a facile and versatile approach for the formation of ball-like polymer–inorganic patchy microcapsules with a tunable shell by combining sol–gel chemistry of silica precursor and phase separation between the polymer and the precursor. Firstly, chloroform-in-water emulsion droplets containing poly(methyl methacrylate) (PMMA), silica precursor [tetraethyl orthosilicate (TEOS)] and co-surfactant sodium dioctyl sulfosuccinate (Aerosol OT or AOT) were prepared by shaking the mixture by hand. Due to the added AOT, water molecules diffuse into the chloroform droplets, and the tiny water droplets would coalesce gradually, triggering the formation of double emulsion droplets. Upon further solvent evaporation, the concentration of the polymer and the silica precursor in the oil shell of the double emulsions increases, leading to the phase separation between the polymer and the precursors (and partially formed silica through the hydrolysis and condensation of TEOS). Because of the confined geometry of the oil shell in the double emulsions, polymeric disc-like structures, stabilized by AOT, were dispersed in the silica precursors. Meanwhile, the silica precursor hydrolyzed and condensed when brought in contact with the aqueous solution, ultimately leading to the formation of a mineralized shell around the polymer domains and the hybrid patchy microcapsules. Effect of synthesis conditions, such as the amount of TEOS, AOT, and PMMA used, the pH value, and solvent evaporation rate on interfacial behavior of the solvent/water; and the morphology of the patchy microcapsules were investigated. Patchy microcapsules with tunable patch size and shape can be generated through tailoring the experimental parameters. Our study indicates that the hybrid patchy microcapsules can be formed by taking advantage of the sol–gel chemistry and the phase separation process, and the underlying generality of the synthesis procedure allows for a variety of applications, including drug storage, coatings, delivery, catalysis, and smart building blocks in self-assembling systems.     

Chloroform Emulsions Containing TEOS,APS and DTSACl as Cores for Microencapsulation

The method of preparation of microcapsules having liquid cores and hydrolyzed silica shells was demonstrated. Microcapsules were obtained by hydrolysis and condensation of silica sources contained in emulsion droplets. Tetraethyl orthosilicate {TEOS), (3 - Aminopropyl)triethoxysilane (APS) and Dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (DTSACl) were used as silica sources. The interfacial properties of chloroform-TEOS(APS, DTSACl)/surfactant solution systems were investigated to determine the conditions favourable for emulsification. Emulsions were prepared using evaporation technique and stabilized, if it was necessary, by addition of TWEEN 80. Droplet size distribution, zeta potential and stability of emulsions were examined.     

Preparation of monodisperse PMMA microspheres using 2-vinyl-4,4′-dimethylazlactone as a particle Stabilizer

Polymeric microspheres of methyl methacrylate (PMMA) have been prepared via emulsion polymerization using potassium persulfate as initiator. The polymeric spheres were also prepared with varied concentration of an additional component, 2-vinyl-4,4′-dimethylazlactone (VDMA), which greatly affected the properties of the spheres. NMR analysis indicates the presence of VDMA in the polymer particles, and FT-IR analysis shows hydrolysis of VDMA in the polymer which produced N-acryloylmethylalanine, (NAMA). The VDMA hydrolysis thus led to carboxyl functionality which served to stabilize the microspheres during the emulsion polymerization showing a significant effect on particle size, distribution, and morphology, but little effect on molecular weight or thermal properties of the polymer. Also the effect of varying the concentration of initiator (potassium persulfate, KPS) was investigated, and had little effect on particle size or distribution or molecular weight of the polymer particles.     

A novel approach to produce monodisperse hollow pure silica spheres

In this work, we report an efficient method to produce pure hollow silica spheres (HSS) using phenyltrimethoxysilane (PTMS) compound. The production of HSS was carried out via hydrolysis of PTMS in the aqueous media and followed by a condensation reaction to form silica spheres with phenyl groups. The product was then calcined to remove phenyl groups and obtain pure silica spheres with >95% fine structure. The chemical nature of pure silica was confirmed by Fourier transforms infrared spectroscopy. The calcined HSS were stable beyond the temperature of 900 °C as confirmed by thermal gravimetric analysis (TGA). The calcined spheres preserved their spherical appearance and hollow core as shown by SEM and TEM micrographs. Interestingly, the average size of the spheres was reduced significantly after calcination from 760 to 510 nm, confirming further the removal of phenyl groups. The calcined HSS offered much higher surface area (A_s) when analysed by BET; A_s for calcined product was ～406 and mere ～4.8 m²/g for uncalcined HSS. Finally, drug release study of cisplatin/HSS showed over 45% of steady cumulative release for 72 h. The prepared HSS can be dispersed in water opening the possibility of many novel bio/non-bio applications.     

Synthesis of micrometer-sized hard silica spheres with uniform mesopore size and textural pores

Micrometer-sized silica spheres were prepared using a new pH-induced rapid colloid aggregation method in water-in-oil (W/O) emulsion separately with F127 and the mixture of Pluronic triblock copolymer (F127, P123, or P105) and PEG20000 as templates. All the mesoporous silica spheres exhibited high surface areas (657-1145 m2/g) and large pore volumes (0.46-2.16 ml/g). Through optimizing the synthetic conditions, hard silica spheres with narrow particle size distribution, uniform pore size, and textural pores were obtained. Finally, the mechanism of this synthetic route is discussed.     

CdSe/CdS/SiO2复合纳米球的制备及发光性能

采用两相法合成了CdSe/CdS核-壳结构的量子点, 用氨水催化水解正硅酸乙酯制得复合结构的CdSe/CdS/SiO₂发光纳米球. 通过对量子点用量、氨水用量、反应时间及溶剂比例等实验条件的调节, 得到了单分散性较好, 尺寸在23~145 nm的复合发光纳米球. 利用紫外-可见吸收光谱和荧光发射光谱对其发光性能进行了研究, 同时利用透射电镜(TEM)观察复合纳米球的形貌. 结果表明, 复合发光纳米球样品的最高荧光量子产率可达8%.     

Preparation of Silica/Poly(tert‐butylmethacrylate) Core/Shell Nanocomposite Latex Particles

Nanocomposite latex particles, with a silica nanoparticle as core and crosslinked poly(tert‐butylmethacrylate) as shell, were prepared in this work. Silica nanoparticles were first synthesized by a sol‐gel process, and then modified by 3‐(trimethoxysilyl)propyl methacrylate (MPS) to graft C?C groups on their surfaces. The MPS‐modified silica nanoparticles were characterized by elemental analysis, FTIR, and ²⁹Si NMR and ¹³C‐NMR spectroscopy; the results showed that the C?C groups were successfully grafted on the surface of the silica nanoparticles and the grafted substance was mostly the oligomer formed by the hydrolysis and condensation reaction of MPS. Silica/poly(tert‐butylmethacrylate) core/shell nanocomposite latex particles were prepared via seed emulsion polymerization using the MPS‐modified silica nanoparticle as seed, tert‐butylmethacrylate as monomer and ethyleneglycol dimethacrylate as crosslinker. Their core/shell nanocomposite structure and chemical composition were characterized by means of TEM and FTIR, respectively, and the results indicated that silica/poly(tert‐butylmethacrylate) core/shell nanocomposite latex particles were obtained.     

One-step synthesis of highly monodisperse hybrid silica spheres in aqueous solution

An effective and reproducible method of preparing highly monodisperse organic-inorganic hybrid silica spheres was studied. One process, one precursor (organosilane) and one solvent (water) were used in our experiments. The size of hybrid silica spheres could be adjusted from 360 to 770 nm with relative standard deviation below 2% by controlling the concentration of the organosilane precursor and the ammonia catalyst. The increasing of the precursor concentration increases the particle size while the catalyst concentration has a reverse effect on the particle size. The concept of homogeneous nucleation and growth processes are introduced to explain the formation mechanism and the effect of reaction conditions. The scanning electron microscopy (SEM) images illustrate the copiousness in quantity and the uniformity in size/shape of the particles that could be routinely accomplished in this synthesis. Fourier transform infrared (FT-IR) and (29)Si nuclear magnetic resonance (NMR) spectra confirm the structure of vinyl hybrid silica spheres, where the vinyl group (-CH=CH(2)) exists and connects to the silicon atom. This method has also been extended to design and prepare other organic-inorganic hybrid materials especially in monodisperse surface-modified silica spheres.     

Synthesis of spherical submicron-sized magnetite/silica nanocomposite particles

This paper describes a method for fabricating spherical submicron-sized silica particles that contained magnetite nanoparticles (magnetite/silica composite particles). The magnetite nanoparticles with a size of ca. 10 nm were prepared according to the Massart method, and were surface-modified with carboxyethylsilanetriol. The fabrication of magnetite/silica composite particles was performed in water/ethanol solution of tetraethoxyorthosilicate with ammonia catalyst in the presence of the surface-modified magnetite nanoparticles. The magnetite/silica composite particles with a size of ca. 100 nm were successfully prepared at 0.05 M TEOS, 15 M water, and 0.8 M ammonia with injection of the magnetite nanoparticle colloid at 2 min after the initiation of hydrolysis reaction of TEOS. Magnetite concentration in the composite particles could be raised to 17.3 wt.% by adjustment of the injected amount of the magnetite colloid, which brought about the saturation magnetization of 7.5 emu/g for the magnetite/silica composite particles.     

高分散性SiO2/PMMA复合材料的制备与表征——纳米SiO2在MMA中的分散

用硅烷偶联剂3-(甲基丙烯酰氧)丙基三甲氧基硅烷(MPS)对分散于乙醇中的纳米SiO2进行偶联改性,再通过介质置换和原位本体聚合制得SiO2/甲基丙烯酸甲酯(MMA)单体分散液和SiO2/PMMA复合材料.红外光谱分析(FTIR)和热重分析(TG)结合洗提实验考察了SiO2表面MPS的偶联率和偶联效率,透射电镜(TEM...     

Hierarchical Porous Polymer Beads Prepared by Polymerization-induced Phase Separation and Emulsion-template in a Microfluidic Device

Porous polymer beads（PPBs） containing hierarchical bimodal pore structure with gigapores and meso-macropores were prepared by polymerization-induced phase separation（PIPS） and emulsion-template technique in a glass capillary microfluidic device（GCMD）. Fabrication procedure involved the preparation of water-in-oil emulsion by emulsifying aqueous solution into the monomer solution that contains porogen. The emulsion was added into the GCMD to fabricate the（water-in-oil）-in-water double emulsion droplets. The flow rate of the carrier continuous phase strongly influenced the formation mechanism and size of droplets. Formation mechanism transformed from dripping to jetting and size of droplets decreased from 550 μm to 250 μm with the increase in flow rate of the carrier continuous phase. The prepared droplets were initiated for polymerization by on-line UV-irradiation to form PPBs. The meso-macropores in these beads were generated by PIPS because of the presence of porogen and gigapores obtained from the emulsion-template. The pore morphology and pore size distribution of the PPBs were investigated extensively by scanning electron microscopy and mercury intrusion porosimetry（MIP）. New pore morphology was formed at the edge of the beads different from traditional theory because of different osmolarities between the water phase of the emulsion and the carrier continuous phase. The morphology and proportion of bimodal pore structure can be tuned by changing the kind and amount of porogen.     

Size control of giant unilamellar vesicles prepared from inverted emulsion droplets

The production of giant lipid vesicles with controlled size and structure will be an important technology in the design of quantitative biological assays in cell-mimetic microcompartments. For establishing size control of giant vesicles, we investigated the vesicle formation process, in which inverted emulsion droplets are transformed into giant unilamellar vesicles (GUVs) when they pass through an oil/water interface. The relationship between the size of the template emulsion and the converted GUVs was studied using inverted emulsion droplets with a narrow size distribution, which were prepared by microfluidics. We successfully found an appropriate centrifugal acceleration condition to obtain GUVs that had a desired size and narrow-enough size distribution with an improved yield so that emulsion droplets can become the template for GUVs.