Preparation and properties of organic–inorganic hybrid gel films based on polyvinylpolysilsesquioxane synthesized from trimethoxy(vinyl)silane

Polyvinylpolysilsesquioxane (PVPS) organic–inorganic hybrid gel films comprising polyethylene and siloxane backbone linkages were prepared through two routes: trimethoxy(vinyl)silane (VTS) was first subjected to radical polymerization of the vinyl groups, followed by acid‐catalyzed hydrolytic polycondensation of the trimethoxysilyl groups (route A) to afford PVPS; in the second route PVPS was prepared in reverse order (route B). PVPS gel films were transparent and homogeneous. We find that the mechanical and heat‐resisting properties correlate both to the degree of polymerization and the degree of cross‐linking. Copyright © 2003 John Wiley & Sons, Ltd.     

Preparation of Silica-Gel Film with pH Indicators by the Sol–Gel Method

Gel films with various pH indicators were prepared by the sol–gel method without catalysts. The obtained gel films showed good response for various pH solutions as optical pH sensors and no leaching of the indicators was observed. The feature of absorption spectra of the indicators in the gel films was almost the same as that in the aqueous solutions. pKa of the indicators in the gel films was shifted with the increase of the TMOS content in the starting solutions. These results suggest that the pH indicators in the gel films were trapped in similar environment as in the solutions.     

Use of a self-assembling organogel as a reverse template in the preparation of imprinted porous polymer films

The concept of reverse templating of an organogel to form imprinted porous divinylbenzene polymer films with submicrometer channels is demonstrated. The organogel comprising a 1:1 molar ratio of two organogelators, that is, bis(2-ethylhexyl) sodium sulfosuccinate and 4-chlorophenol, was formed in divinylbenzene. The gel was cast as a thin film before UV polymerization of the solvent, and the organogelators were later removed by simple washing with water and isooctane. The integrity of the fiber bundles of the organogel was preserved during polymerization, and an exact hollow replica was obtained after the organogelators were leached away. It is easily possible to imprint gel fiber bundle structures into polymeric films through this technique. The gel can also be formed on macroporous substrates to yield supported thin porous polymeric films. With the incorporation of functional nanoparticles in AOT inverse micelles and hence the organogel, nanoparticle-containing porous polymer films exhibiting luminescence or magnetic properties are envisioned.     

聚苯胺对新型杂化透明导电薄膜制备和性能的影响

以聚苯胺和掺锑的氧化锡作为主要原料, 采用溶胶-凝胶法制备了新型有机-无机杂化透明导电薄膜. 薄膜的可见光透过率为85%以上, 电导率达到10⁰～10¹ S•cm^－1. 研究了聚苯胺含量的变化对浸涂液粘度、薄膜结构、光透过率、电导率的影响. 随着聚苯胺引入量的增加, 薄膜的电导率、可见光透过率均有所增大. 浸涂液的粘度可在长达25天的时间内保持稳定, 很适于浸涂工艺. 扫描电镜照片显示, 薄膜比较致密、均匀, 厚度为250 nm左右.     

The Role of 2-(Methacryloyloxy) Ethyl Acetoacetate in the Polymerization of Hybrid Multicomponent (Si, Ti, Zr) Sols

2-(Methacryloyloxy) ethylacetoacetate (MEEAH) was used as stabilyzing agent to control the chemical reactivity of Ti and Zr monomeric alkoxides in a Si—Ti—Zr sol. The organic and inorganic polymerizations were carried out simultaneously. The organic polymerization was performed using benzoyl peroxide as the initiator. The inorganic polymerization was done via the sol-gel process. The polymerization was studied by several spectroscopic techniques, including Fourier Transform Infrared (FTIR), UV-Vis, ²⁹Si NMR, Small Angle X-ray Scattering (SAXS) and X-ray diffraction (XRD). Theoretical calculation and experimental results showed that MEEAH acted as a monodentate ligand, mainly. This led to a high condensation extent of the Si species in the sol. A short range order gel was obtained, according to the SAXS results. The Si—O—Ti and Si—O—Zr bonds were detected by FTIR. The bonds remained stable, because a sample calcined at 1173 K was amorphous according to the XRD results, indicating structural homogeneity.     

Deposition of acrylonitrile cluster ions on solid substrates: thin film formation by intracluster polymerization products

Cluster anions of acrylonitrile (AN), known to give intracluster anionic polymerization products, were deposited on solid substrates. The obtained films were examined by using infrared absorption spectroscopy, X-ray photoemission spectroscopy, and gel permeation chromatography with the aid of quantum chemical calculations. The acquired spectroscopic data are similar to those of polyacrylonitrile (PAN), while the normal polymerization of AN or reactions related to PAN seemed not to occur noticeably. On the contrary, the product analysis shows that most of the constituent molecules of the films are formed via cyclohexane-1,3,5-tricarbonitrile (CHTCN), a dominant product of the intracluster polymerization of AN, accompanied by fragmentation and dimerization.     

Chain transfer agents in cationic photopolymerization of a bis‐cycloaliphatic epoxide monomer: Kinetic and physical property effects

The effects of chain transfer agents (CTA) on cationic ring‐opening polymerization of 3,4‐epoxycyclohexylmethyl‐3′,4′‐epoxycyclohexane carboxylate (EEC) were explored. EEC was polymerized in the presence of various CTAs, and epoxide conversions monitored via Raman spectroscopy. Polymer films were prepared and analyzed by dynamic mechanical analysis. Many of the organic alcohols studied greatly enhanced epoxide polymerization rates and conversion levels. The gel fraction of polymer specimens decreased rapidly with increasing amounts of octanol (gel fraction >90% up to 0.3 equiv OH) but remained high with increasing amounts of 1,2‐propanediol (gel fraction >90% up to 0.6 equiv OH). Increasing the size of primary alcohols had little effect on the polymerization rates and conversions. The polymerization rate decreased with increasing alcohol substitution (1°>2°>3°). Acidic alcohols had very low impact on conversion and polymerization rates relative to the neat epoxy resin. The glass transition temperature was inversely related to the size and amount of CTA. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Preparation of PZT Thick Films by an Interfacial Polymerization Method

Pb(Zr_0.53Ti_0.47)O₃ (PZT) films of 10 to 50 m in thickness were prepared by a new sol-gel process using an interfacial polymerization technique. The interfacial polymerization process is that an alkoxide precursor solution is poured on the surface of water in a container to form a gel film at the interface between the two immiscible liquids. The precursor solution was prepared by adding PZT alkoxide solution, PZT powders coated with Pb₅Ge₃O₁₁ (PG), and a surfactant into hexane solvent. After the polymerization at the interface, the gel films were gently placed on a silicon substrate by draining the water in the container. The gel films containing PZT powders were sintered at 950°C for 10 min to obtain crystallized PZT films. The remanent polarization of a PZT thick film was 33.1 C/cm². The piezoelectric d ₃₃ constant measured with a Mach-Zehnder interferometer was 225 pm/V and was independent of frequency from 0.2 to 3 kHz.     

Preparation of poly(methyl methacrylate) films containing silica particle array structure from colloidal crystals

The incorporation of monodisperse, polymer-modified silica into poly(methyl metharylate) to prepare polymer films containing particle array structure was investigated. The preparation was carried out by a two-step radical polymerization for gelation and solidification. The colloidal crystallization of poly(methyl metharylate)-modified silica, in 78 nm size, in acetonitrile and successive copolymerization of methyl methacrylate and 1,2-dimethacryloylethane by UV light irradiation gave the polymer gel containing the colloidal crystal structure. The exchange of acetonitrile in the gel with methyl methacrylate and further photo-radical polymerization gave the durable polymer film composed of silica particle array.     

表面分子印迹高分子膜修饰硅胶用于血清中茶碱的固相萃取

采用表面引发可逆加成-断裂链转移自由基聚合反应,在硅胶表面修饰了分子印迹高分子膜(MIP-silica)。以元素分析和氮吸附分析对修饰的分子印迹高分子膜进行了表征。与传统采用本体聚合合成的分子印迹高分子相比,MIP-silica具有更好的传质能力。本文合成的茶碱印迹MIP-silica可以作为选择性固相萃取材料从血清中富集、检测微量的茶碱,该法合成的MIP-silica还可用于高效液相色谱和毛细管电色谱等领域。     

Preparation of Fluorine-Containing Polyacrylate Emulsion by a UV-initiated Polymerization

A fluorine-containing polyacrylate emulsion was synthesized by a UV-initiated emulsion polymerization from methyl methacrylate (MMA) and hexafluorobutly methacrylate (HFMA) in the presence of 2-hydroxy-4-(2-hydroxyethoxy)-2-methyl-propiophenone (Irgacure 2959) as a hydrophilic photoinitiator at room temperature. The latex and films were characterized by Fourier transformed infrared (FT-IR) spectrometry, nuclear magnetic resonance (¹H-NMR, ¹⁹F-NMR) spectrometry, transmission electron microscopy (TEM), recycling gel permeation chromatography (GPC), dynamic light scattering (DLS), and contact angle (CA) analysis, respectively. The effects of photoinitiator and emulsifier concentration on the polymerization were discussed. Compared to the corresponding thermal polymerization, UV-initiated polymerization of the MMA/HFMA emulsion could be accomplished at a much higher speed. The polymerization conversion in UV-initiated polymerization reached 95% within 10 min at an emulsifier concentration of 0.6 wt%, photoinitiator concentration of 0.4 wt%, and monomer concentration of 10 wt%.     

Acrylic polymer/silica hybrids prepared by emulsifier‐free emulsion polymerization and the sol–gel process

Acrylic polymer/silica hybrids were prepared by emulsifier‐free emulsion polymerization and the sol–gel process. Acrylic polymer emulsions containing triethoxysilyl groups were synthesized by emulsifier‐free batch emulsion polymerization. The acrylic polymer/silica hybrid films prepared from the acrylic polymer emulsions and tetraethoxysilane (TEOS) were transparent and solvent‐resistant. Atomic force microscopy studies of the hybrid film surface suggested that the hybrid films did not contain large (e.g., micrometer‐size) silica particles, which could be formed because of the organic–inorganic phase separation. The Si? O? Si bond formed by the cocondensation of TEOS and the triethoxysilyl groups on the acrylic polymer increased the miscibility between the acrylic polymer component and the silica component in the hybrid films, in which the nanometer‐size silica domains (particles) were dispersed homogeneously in the acrylic polymer component. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 273–280, 2006     

Effects of ethylene glycol dimethacrylate as cross-linker in ionic liquid gel polymer electrolyte based on poly(glycidyl methacrylate)

In this study, modified poly(glycidyl methacrylate)-based films for gel electrolyte were prepared by an in situ UV photopolymerization technique. The effects of adding ethylene glycol dimethacrylate (EGDMA) to the polymer host were studied through X-ray diffraction analysis and differential scanning calorimetry. The results from Fourier transform-infrared spectra indicate complete polymerization among the monomers. The addition of EGDMA to the formulation of gel polymer electrolyte increased the loading of 1-butyl-3-methylimidazolium bis(fluoromethylsulfonyl)imide up to 200 wt.% with the highest value of 8.2 × 10^?4 S cm^?1. All the gel polymer electrolyte membranes obeyed the Arrhenius law.     

Synthesis and Nonlinear Optical Susceptibility of Cyanine Dye J-Aggregate Doped Silica Film (I)

We synthesized thin silica films doped with condensed J aggregates of pseudisocyanine dyes (PIC) as a material for nonlinear optical devices by simple sol-gel processing and spincasting. The sol and the silica films were characterized with UV-visible absorption spectroscopy, fluorescence spectroscopy and fluorescence microscopy. The films contain plenty J aggregates, and are optically transparent and stable at room temperature. J aggregation dependence on dye concentration in the sol and spin speed during spincasting were investigated. It was found that dye condensation in the sol solution and fast spinning promote the formation of J aggregates in the films. Because of the high third order nonlinear susceptibility around 10^–7 esu, the films are expected to be useful for non-linear optical devices.     

Influence of Particle Nucleation in Pressure Sensitive Adhesive Properties: Miniemulsion versus Emulsion Polymerization

Miniemulsion polymerization is a promising approach to produce and tailor pressure sensitive adhesives (PSAs). In this paper, a systematic comparison of the adhesive properties of latexes produced by miniemulsion and conventional emulsion polymerization is presented. Specifically, the influence of the total surfactant concentration, chain transfer agent concentration and chemical composition on the final adhesive properties of the polymer 2-ethyl hexyl acrylate/methyl methacrylate/acrylic acid was discerned using a 2³ factorial design for each polymerization method. In addition to the adhesive properties (i.e., loop tack, peel strength and shear strength), molecular weight distribution, particle size distribution (PSD) and glass transition temperature were analyzed. The results show that under the conditions used in this work, it is possible to produce PSAs using miniemulsion polymerization, a process wherein monomer droplet nucleation is the dominant particle nucleation mechanism. The use of a miniemulsion polymerization process, as opposed to the conventional emulsion technique, produced several differences such as larger particles sizes and narrower molecular weight distributions. Focusing on the PSA films that exhibited adhesive rather than cohesive failure, the PSA films generated via miniemulsion polymerization displayed higher values of loop tack and peel strength compared to those produced via conventional emulsion polymerization. Shear strength results were strongly dependent on the amount of gel content and sol molecular weight for both cases.     

Thiol-ene UV-curable coatings using vegetable oil macromonomers

Allyl, acrylate, and vinyl ether derivatives of castor oil were synthesized and blended with multifunctional thiols for evaluation as thiol-ene ultraviolet (UV) curable systems. The UV cured films were characterized and evaluated via ASTM tests, gel content, and dynamic mechanical analysis (DMA) as a function of time. Fourier transform infrared spectroscopy and DMA studies established that property advancement resulted from auto-oxidation, continued thiol-ene polymerization, or a combination of both mechanisms.     

In situ sol–gel preparation of high transparent fluorinated polyimide/nano-MgO hybrid films

Hybrid nanocomposite films of magnesium oxide (MgO) in fluorinated polyimide (PI) from 4, 4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 4, 4′-Diaminodiphenyl ether (ODA) have been successfully fabricated via an in situ sol–gel polymerization technique. The MgO content in hybrid films was varied from 0 to 5 wt%. The hybrid films were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), ultraviolet–visible (UV–Vis) spectroscopy and thermal gravimetric analyses (TGA). The results of FTIR, XRD and FESEM showed that the MgO nanoparticles were well dispersed in the polymer matrix due to the coordination between the carbonyl group of polymers and Mg atom, and the as-prepared hybrid films exhibited excellent optical transparency in the visible region and good UV-shielding properties in the UV region. Although the thermal stability of the hybrid films is slight inferior to pure PI, it is still good for the practical application below the temperature of 300 °C.     

Synthesis and Properties of Cross-Linked 4-Vinylpyridine-Styrene-Halogen Complexes

Cross-linked 4-vinylpyridine-styrene beads (PVPS) containing various amounts of pyridine rings were synthesized and reaction with methyliodide and peroxyacetic acid gave corresponding N-methylpyridinium salts and N-oxides with more than 92% of the pyridine rings being transformed. PVPS formed stable complexes with bromine and chlorine in the ratio 1:1, and when a higher amount of halogen was used, complexes with two molecules of halogen on each pyridine were formed. Similar complexes were also formed with PVPS-N-oxides in the presence of bromine and chlorine, while the reaction of PVPS-hydrohalide with bromine and chlorine resulted in hydrobromide perbromide and hydrochloride perchloride resins. The chemical activity of halo-substituted resins was tested in the reaction with 1,1-diphenylethylene. Chi or o-substituted resins are very stable, while bromo-substituted beads gave bromoalkene, dibromide, and alkoxybromide, depending on the structure of the reagent, solvent, and reaction temperature.     

柱状相聚苯乙烯-b-聚乳酸的合成及引导组装

设计并合成了2种柱状相结构的聚苯乙烯-b-聚乳酸(PS-b-PLA)两嵌段共聚物,并表征了它们在化学图案上的引导自组装行为。在辛酸亚锡(Sn(Oct)_2)催化下,采用羟基官能化的聚苯乙烯(PS-OH)大分子引发剂分别引发外消旋丙交酯(rac-LA)和左旋丙交酯(L-LA)开环聚合,制备了两个相对分子质量相近但构型不同的PS-b-PLA:PS-b-PDLLA和PS-b-PLLA。通过核磁共振波谱仪(NMR)、凝胶渗透色谱仪(GPC)、示差扫描量热仪(DSC)、热重分析仪(TGA)、小角X射线衍射仪(SAXS)等测试手段对两个嵌段共聚物的性质进行了表征。然后,将PS-b-PDLLA和PS-b-PLLA薄膜在六方点阵化学图案模板上加热引导自组装,得到长程有序排列的六方柱状相结构。相对于柱状相的PS-b-PLLA,柱状相的PS-b-PDLLA具有较大的拉伸比例,可以在更大的周期范围内组装出规整的六方结构。这一结果与层状相PS-b-PDLLA和PS-b-PLLA薄膜在线性化学图案上组装的结果相似。     

Synthesis of star-shaped polyhedral oligomeric silsesquioxane (POSS) fluorinated acrylates for hydrophobic honeycomb porous film application

Two different eight-arm star-shaped polyhedral oligomeric silsesquioxane (POSS) fluorinated acrylates were synthesized through atom transfer radical polymerization (ATRP) and applied for hydrophobic honeycomb-patterned porous films through the breath figure (BF) method. The structure of polymers was characterized by Fourier transform infrared (FT-IR) spectroscopy, nuclear magnetic resonance (NMR), and gel permeation chromatography (GPC), and surface analysis was featured by X-ray photoelectron spectroscopy (XPS). Depending on the influences of polymer architectures, solvents utilized, and solution concentrations, honeycomb-patterned porous films were obtained. It could be found that the introduction of fluorine components was a favorable condition for BF formation and chloroform (CHCl₃) utilized as solvent with an appropriate concentration of 30 mg/mL was the best condition for these hydrophobic honeycomb-patterned porous films. Meanwhile, the obtained honeycomb films could be retained after long-time preservation in an acid-base condition, which shows a great potential in filtration, cell culture, tissue engineering, and marine antifouling applications.