Barrier Properties OF Inorganic-Organic Polymers: Influence of Starting Compounds,Curing Conditions and Storage-Scaling-Up to Industrial Application—

With a new kind of barrier coating material, namely inorganic-organic polymers, it is possible to obtain high-barrier properties for oxygen, water vapor, and flavor permeation. These hybrid polymers can be synthesized by the sol-gel technique. Network forming reactions and degrees of condensation in the coating sols as well as in the cured coating materials were characterized using ²⁹Si, ¹³C-NMR and FT-Raman spectroscopy. The oxygen barrier properties of the hybrid polymers were found to be strongly influenced by the inorganic and also by the organic network density. In order to scale-up the excellent laboratory results to pilot plant and production dimensions additional efforts were necessary. For optimization of the barrier coating compositions the influence of the starting compounds on the resulting barrier properties had to be investigated. A constant quality of the coating sols during the industrial processing had to be guaranteed so as to obtain reproducible barrier properties. The influence of storage conditions on chemical reactions in the coating sols, indicated by changes of viscosity, was investigated. Since the curing times of the laboratory system were not transferable to the high speed of the production roll coating process more effective curing methods had to be found. The influence of the storage time of the cured coating materials on the oxygen barrier properties was investigated. Even by storing at ambient temperature further improvement of the oxygen barrier properties was obtained. Only by optimizing all of the above mentioned parameters can the excellent barrier properties result in marketable products.     

Ultrathin Silicon-Compound Barrier Coatings for Polymeric Packaging Materials: An Industrial Perspective

Growing demands for increased shelf-life of food products and chemical inertia of the contact surfaces have stimulated development of polymers with improved high-barrier properties. Our objectives in this article are (1) to describe experimental results on Plasma-enhanced chemical vapor deposition (PECVD) and its importance to produce thin layers of inorganic glassy barrier materials for food, pharmaceutical, and organic display applications; (2) despite the thereby greatly enhanced quality of film or rigid packaging material, some residual coating defects result in less-than-perfect gas, moisture and aroma barriers: an innovative technique based on reactive ion etching (RIE) in oxygen plasma is also presented, along with a staining method, which render even sub-m coating defects visible. Data are shown for oxygen transmission rate on virgin and defective coatings, and the industrial context and applications are presented.     

Development of Passive and Active Barrier Coatings on the Basis of Inorganic–Organic Polymers

Summary. With a new kind of barrier coating material, namely inorganic–organic polymers, it is possible to obtain excellent barrier properties against oxygen, water vapor, and flavor permeation. These hybrid polymers can be synthesized by the sol–gel technique. If extremely low permeation values are needed, the combination of hybrid polymer coatings with thin inorganic oxidic layers (SiO_x, AlO_x) is very effective and leads to permeation values for oxygen and water vapor below 10⁻³ cm³/m² · d · bar or g/m² · d. These passive barrier layers can be further improved by the combination with active oxygen barrier layers which have been developed for the food packaging industry. This approach makes these multilayer laminates promising candidates for special applications in the food packaging industry as well as for sophisticated applications in technical areas: the encapsulation of sensitive organic devices like solar cells, organic light emitting diodes, or polymer electronic systems.     

Inorganic-Organic Polymers as Migration Barriers Against Liquid and Volatile Compounds

In addition to the barrier properties against water vapor and oxygen, inorganic-organic polymers can also function as protection layers against unwanted migration of chemical substances in two ways. First, hybrid polymers prevent components from migrating out of polymer substrates. This is of special interest for polymeric materials containing substances like plasticizing agents, unreacted monomers or catalysts. Thus the olfactory nuisance and the toxicological emission are decreased. The plastics are also prevented from becoming prematurely brittle. Second, the coated materials are also protected against the interaction of dyes or dirt staining the material.These functions can be achieved by thermally or UV curable coating materials, synthesized by the sol-gel technique. Since several polymer materials show only a low heat resistance (e.g. PVC, polyolefines), this publication is focussed on the development of new migration barriers based on photochemically curable sols.Another advantage of the UV process in comparison to thermal treatments are the short curing times and low power consumption which make this process even more attractive for industrial applications. The coatings were characterized by IR and solid state NMR spectroscopy. The migration barrier properties were tested according to industrial standards.Due to the choice of specific functional groups, these hybrid polymers can be further modified in order to combine the migration barrier function with additional properties: scratch and abrasion resistance, hydrophobicity, antistatic effects. Examples of feasible combinations of properties are also given.     

Effect of photoinitiator on photopolymerization of inorganic–organic hybrid polymers (ORMOCER®)

Inorganic–organic hybrid polymers have been developed and tested for evaluation in optical and electrical applications. Although hybrid inorganic–organic polymers can be synthesized by sol–gel chemistry at first, the physical properties of hybrid inorganic–organic polymers are changed during thin film-making processes, that is, photocuring and thermal curing. To investigate the effect of photoinitiator on the material properties during processing, a model system containing methacrylic groups as organically polymerizable units was selected. The conversion of CC double bond of methacrylic groups depending on some kinds of photoinitiator quantities was characterized by Fourier transform infrared spectroscopy. It was confirmed to correlate the degree of CC double bond conversion with the refractive indices. Thermodynamically, the enthalpy of the photopolymerization of hybrid polymer was investigated by UV–DSC. UV–DSC spectra showed the exothermic nature of photopolymerization of ORMOCER® to be in dependence of photoinitiator quantities. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1979–1986, 2004     

无机/有机杂化IPN的合成与表征

随着互穿聚合物网络(IPN)的发展,出现了无机/有机杂化IPN,调整两组分或多组分互穿程度控制材料的结构、形态与性能,可使材料具有较宽的适用范围.此类材料具有高模量、高韧性,易成型加工.     

Investigations on aromatic polyesters with polynaphthalene systems in the main chain. I. Low-temperature solution polycondensation

A series of aromatic polyesters has been prepared by low-temperature solution polycondensation of derivatives of dihydroxydinaphthyl or dihydroxydinaphthylmethane with terephthaloyl chloride. The chemical, physical, and thermal properties of some polyesters have been investigated. Some of the polyesters obtained have high melting temperatures (340–420°C) and very good thermal resistance. In spite of their high melting temperatures some polymers give solutions in organic solvents which make it possible to produce films and coatings with good dielectric and mechanical properties and with a relatively high thermal resistance.     

Synthesis, characterization and flame retardant of UV-curable hybrid coatings containing SiO2–P2O5–B2O3 via sol–gel method

A ternary sol containing silicon, phosphorus and boron modified by ??-methacryloxypropyltrimethoxysilane was synthesized by sol?Cgel method. The ternary sol was incorporated into the organic matrix and UV-curable organic/inorganic hybrid coating materials were obtained. Hardness, transmittance, haze, cross-cut adhesion and abrasion resistance results showed that the mechanical properties of the hybrid coatings improved effectively with no comprising on optical properties by increasing sol content. Scanning electron microscopy and Energy Dispersive X-ray spectrometer studies indicated that inorganic particles were homogenously dispersed in the organic matrix. The flame retardancy of the UV-curable coatings was investigated by thermogravimetric analysis and microscale combustion calorimeter. The results showed that the incorporation of sol into the organic network led to an improvement in the thermal stability and flame retardancy of the hybrid coating materials. It is a desirable achievement to improve simultaneously both flame retardancy and mechanical properties of the coatings.     

Inorganic–organic sol gel hybrid coatings for corrosion protection of metals

Inorganic–organic hybrid coatings by sol–gel process are very suitable for fighting corrosion. Inorganic sols in hybrid coatings not only increase adhesion by forming chemical bonds between metals and hybrid coatings, but also improve comprehensive performances of polymer in the coatings. Different organic polymers or organic functionalities are introduced into gel network to achieve tailored properties, such as hydrophobic properties, increasing cross-linking density, etc. As for corrosion protection of metals organic components of hybrid coatings are selected to repel water and form dense thick films and reduce coating porosity. The factors, such as the ratio of inorganic and organic components, cure temperature, pigments in hybrid coatings, need to be optimized for attaining hybrid films with the maximum corrosion resistance. Electro-deposition technique offers relatively thick homogeneous defect-free hybrid coatings in comparison to dip or spin coating techniques. Green cerium ions and non-ionizable organic inhibitors are more developed in hybrid coatings nowadays than other corrosion inhibitors. Long-term corrosion resistance techniques of inhibitors are discussed. The inhibitors entrapped in the nanocontainers are doped in hybrid films to prolong release of the inhibitors to damaged zones, which is discussed in detail. Among all the nanocontainers of corrosion inhibitors the prospective techniques which show superior corrosion protection are cyclodextrin/organic inhibitor inclusion complexes and layer by layer assembly of organic corrosion inhibitors in nanocontainers. Super-hydrophobic property of hybrid coatings derives from low surface tension and surface roughness of hybrid coatings, which endues the films with excellent corrosion protection for metals, but the durable property of super-hydrophobic coatings needs to be improved for industrial application. An ideal multiple model of hybrid coatings for superior anti-corrosion of metals proposed is a combination of super-hydrophobic hybrid coatings and underlying hybrid coatings doped with sustained release of corrosion inhibitors on metal substrates.     

Synthesis and characterization of UV‐curable phosphorus containing hybrid materials prepared by sol–gel technique

In this study, a series of ultraviolet (UV)‐curable organic–inorganic hybrid coating materials containing phosphorus were prepared by sol–gel approach from acrylate end‐capped urethane resin, acrylated phenyl phosphine oxide oligomer (APPO), and inorganic precursors. TEOS and MAPTMS were used to obtain the silica network and Ti:acac complex was employed for the formation of the titania network in the hybrid coating systems. Coating performance of the hybrid coating materials applied on aluminum substrates was determined by the analysis techniques, such as hardness, gloss, impact strength, cross‐cut adhesion, taber abrasion resistance, which were accepted by international organization. Also, stress–strain test of the hybrids was carried out on the free films. These measurements showed that all the properties of the hybrids were enhanced effectively by gradual increase in sol–gel precursors and APPO oligomer content. The thermal behavior of the hybrid coatings was investigated by thermogravimetric analysis (TGA) analysis. The flame retardancy of the hybrid materials was examined by the limiting oxygen index (LOI); the LOI values of pure organic coating (BF) increased from 31 to 44 for the hybrid materials containing phosphorus (BF‐P:40/Si:10). The data from thermal analysis and LOI showed that the hybrid coating materials containing phosphorus have higher thermal stability and flame resistance properties than the organic polymer. Besides that, it was found that the double bond conversion values for the hybrid mixtures were adequate in order to form an organic matrix. The polycondensation reactions of TEOS and MAPTMS compounds were also investigated by ²⁹Si‐NMR spectroscopy. SEM studies of the hybrid coatings showed that silica/titania particles were homogenously dispersed through the organic matrix. In addition, it was determined that the hybrid material containing phosphorus and silica showed fibrillar structure. Copyright © 2009 John Wiley & Sons, Ltd.     

导电聚合物热电材料研究进展

导电聚合物在室温下具有较高的电导率(σ)、较低的热导率(κ)、柔韧性好、易于合成、原料来源丰富、对环境无污染等优势,是目前最具有热电应用潜力的有机热电材料之一。然而,目前针对导电聚合物作为有机热电材料的相关研究依然处于初级阶段,其在空气气氛中的化学稳定性问题、低的热电优值及尚未完全明确的热电机制一直困扰着研究人员。本文主要针对以上问题,在对前人的研究成果进行综述的基础上对目前有机热电材料所面临的关键问题进行阐述和总结。     

Sol–gel derived organic–inorganic hybrid materials: synthesis,characterizations and applications

Organic/inorganic hybrid materials prepared by the sol–gel approach have rapidly become a fascinating new field of research in materials science. The explosion of activity in this area in the past decade has made tremendous progress in both the fundamental understanding of the sol–gel process and the development and applications of new organic/inorganic hybrid materials. Polymer-inorganic nanocomposite present an interesting approach to improve the separation properties of polymer material because they possess properties of both organic and inorganic such as good permeability, selectivity, mechanical strength, and thermal and chemical stability. Composite material derived by combining the sol–gel approach and organic polymers synthesis of hybrid material were the focus area of review It has also been demonstrated in this review that a more complete understanding of their structure–property behavior can be gained by employing many of the standard tools that are utilized for developing similar structure–property relationships of organic polymers. This review article is introductory in nature and gives introduction to composite materials/nanocomposite, their applications and the methods commonly employed for their synthesis and characterization. A brief literature survey on the polysaccharide templated and polysaccharide/protein dual templated synthesis of silica composite materials is also presented in this review article.     

Preparation and Characterization of the Hybrids Containing Silica Nanoparticles by Sol-Gel Crosslinking Process

The organic/inorganic hybrid nanomaterials containing silica nanoparticles are synthesized by sol-gel crosslinking process. The tetraethoxysilane (TEOS) and γ-aminopropyltriethoxylsilane as coupling agents are used as a precursor. The 2,4,6-tri [(2-epihydrin-3-bimethyl-ammonium)propyl]-1,3,5-triazine chloride (Tri-EBAC) as crosslinking agent is used to form covalent bonds among the inorganic nanoparticles. The chemical and morphological structures of the organic/inorganic hybrid are characterized with FTIR spectra, ²⁹Si-NMR, x-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and atomic force microscope (AFM). The results show that the organic/inorganic hybrid forms covalent bond between the inorganic nanoparticle and Tri-EBAC. The network organic/inorganic hybrid can form good film with even nanometer particles. The network organic/inorganic hybrids nanomaterial not only exhibits the thermal properties of inorganic compounds, but also exhibits the thermal properties of organic polymer.     

Synthesis of polyolefin composition in the presence of supported catalysts

Polyolefins are basic materials in the plastics. Their application is limited by their low thermostability, adhesion, hardness and other physico-mechanical properties. The following treatments are known to improve and modify polyolefin properties: the incorporation of inorganic or organic fillers with a greater hardness and rigidity into the polyolefin matrix, the grafting of functional groups to polyolefins, and crosslinking with the formation of a network structure in the polyolefin matrix. In the case of polymers and inorganic materials, the activation of their surface by the functionalizing and fixing of transition metals allows one to perform polymerization of monomers on a surface to obtain a polymer–polymer composites and a highly filled polymer–inorganic composites.     

网络互穿的固相微萃取聚乙烯醇复合涂层的制备

通过反复冷冻-解冻和溶胶-凝胶方法制备了聚乙烯醇/SiO₂有机/无机双交联网络互穿的固相微萃取涂层, 并利用红外光谱(FTIR)、 热重分析(TGA)、 扫描电子显微镜(SEM)和气相色谱(GC)等方法对该涂层进行了结构及性能表征. 该固相微萃取涂层具有很好的热稳定性(T_d>300 ℃), 通过化学键合作用于玻璃或石英纤维表面, 稳定性好, 不易脱落. 对正丙醇、 正丁醇、 异戊醇和甲苯进行萃取, 结果表明, 该纤维涂层对带有羟基的极性物质有很好的选择性, 并且相对标准偏差(RSD, n=3)小于5.0%.     

Fabrication of transparent Pu/Zro2 nanocomposite coatings with high refractive index

<正>Transparent ZrO_2-polyurethane nanocomposites with high refractive index were prepared by dispersing ZrO_2 nanoparticles in a polyurethane matrix via ligand molecule engineering.TEM showed that the inorganic particles were well dispersed within the polymeric network with no significant macroscopic agglomeration.By controlling the phase separation it was possible to obtain transparent zirconia nanostructured coatings,characterized by improved mechanical and thermal properties.UV-Vis spectra indicated that the coatings still maintained transparency in the visible light.The refractive index of the UV-cured films depends linearly on the ZrO_2 content and varies from 1.475 to 1.625(20 wt%) at 633 nm.These coatings could find advanced applications in coatings of optical and electronic devices.     

Preparation and characters of hyperbranched polyester‐based organic‐inorganic hybrid material compared with linear polyester

To compare the properties of hyperbranched polymers with linear oligomers for preparing organic‐inorganic hybrids, hyperbranched aliphatic polyester (Boltorn^TM H20) and linear polyester hexa‐acrylate (EB830) were selected as organic components for preparing UV‐curable transparent hybrid materials using 3‐(trimethoxysilyl) propylmethacrylate as a coupling agent via a sol‐gel process. The prehydrolyzed product of tetraethoxysilane was used as an inorganic component. The effects of inorganic content on the morphologies, thermal behaviors, photopolymerizaiton kinetics and mechanical properties of the hybrids were investigated. The results show that for hyperbranched polyester‐based hybrids, the organic phase shows much better compatibility with inorganic phase even at high inorganic component content due to its special spheral shape and plenty of functional end groups, compared with linear EB830‐based hybrids. Copyright © 2004 John Wiley & Sons, Ltd.     

UV curing of organic–inorganic hybrid coating materials

The effect of UV-curing time on the mechanism of interaction between the various precursor phases in a novel sol–gel-derived organic–inorganic hybrid coating material and the resulting mechanical and thermal properties of this material when coated onto substrates in thin film form have been examined using a variety of chemical and physical characterisation methods. Microstructurally, the hybrid coating materials examined were all a single amorphous phase and were all optically transparent. The degree of interaction between the organic and inorganic phases, the scratch behaviour of the coating materials and the thermal stability of the coating materials were all found to depend strongly on the UV curing time. For the particular proportions of inorganic and organic components used to make up this hybrid coating material, an optimum UV curing time of 10 min under a UV intensity of 46.3 mW cm⁻² was found to produce transparent coatings which adhered well to the substrates and which were robust in scratch tests on aluminium and polycarbonate substrates and abrasion tests on polycarbonate substrates.     

Preparation of photocurable silica–titania hybrid coatings by an anhydrous sol–gel process

Photocurable silica-titania hybrid coatings were prepared through an anhydrous sol–gel process. Moreover, test samples were prepared by the addition of definite ratios of fluoro acrylate oligomers into the formulations to manage the optical properties of transmitted light. Formulations were applied to corona-treated polycarbonate substrates. Upon adding the inorganic component to the coating material, thermal, mechanical, and other properties, such as hardness, gloss, contact angle, and flame resistance were improved. The photocured hybrid films showed an increase in the refractive index with increasing the titanium tetraisopropoxide content. As expected, a decrease was observed in the refractive index of the coatings with the incorporation of fluoro acrylate resin. The surface morphology of the hybrid films was characterized by ESEM analysis. In addition the chemical composition of the surface of the coatings was identified by ESEM–EDS technique. ESEM studies indicated that inorganic particles were dispersed homogenously throughout the organic matrix.     

Using Taguchi experimental design to reveal the impact of parameters affecting the abrasion resistance of sol–gel based UV curable nanocomposite films on polycarbonate

This work aims at studying the abrasion resistance of differently formulated organic–inorganic hybrid coatings prepared by sol–gel method. The organic phase contained UV curable urethane acrylate oligomers and monomers having different functionalities. The inorganic phase was composed of tetraethyl orthosilicate (TEOS) and 3-methacryloxy propyltrimethoxy silane (MEMO). Through a Taguchi experimental design, the impact of influencing parameters such as molar ratio of precursors, hydrolysis ratio (R), post-curing temperature, post-curing time and weight percentage of inorganic to organic part were investigated. Very high transparency of hybrid coatings indicated that nano sized inorganic phase had formed. MEMO could facilitate the connection of two phases, preventing macro phase separation. However, high levels of MEMO lead to ‘defect structure’ in silica network as well as to decreased transparency and mechanical properties. The optimum condition in which highly transparent films with great abrasion resistance occurred was observed at equimolar ratio of water to alkoxide and TEOS: MEMO ratio being unity. Statistical analysis revealed that thermal post-curing was not significantly important.