超支化聚合物改性环氧树脂的研究进展

超支化聚合物因其独特的结构和性能特点,已在众多领域得到了广泛的应用,尤其是在热固性树脂的改性中的应用,可作为热固性树脂的增韧剂。该文介绍了环氧树脂的性能特点及应用,超支化聚合物的结构及特点,着重论述了近年来超支化聚合物在改性环氧树脂力学性能、固化行为及热性能方面的研究进展,并指出了超支化聚合物在环氧树脂和其它热固性树脂改性方面的发展方向。     

超支化聚酯在环氧树脂改性中的应用

超支化聚合物是一类具有三维树形结构的高度支化的大分子。由于其独特的结构和性能以及可实现工业化生产的潜力,超支化聚合物已经成为高分子材料领域研究的热点之一,并且得到了越来越多的关注。作为一类非常重要的超支化聚合物,超支化聚酯(HBPE)引起了研究人员的极大兴趣。目前,HBPE已经在众多领域获得应用,特别是在环氧树脂改性中的研究发展迅速。综述了HBPE作为改性剂在环氧树脂中的应用研究进展,同时对HBPE在环氧树脂和其他热固性树脂改性中的应用研究方向作了展望。     

Preparation and cured properties of novel cycloaliphatic epoxy resins

Preparation and characterization of novel cycloaliphatic epoxy resins, which are derived from octadienyl compounds, were studied. From a model peracetic acid epoxidation reaction using 2,7-octadienyl acetate-1, the structure of the liquid resins is estimated to be mainly terminal epoxides and some amount of inner epoxide depending on the epoxide content. The epoxy resins offer lower toxicity and lower vapor pressure. The reactivity of the resin with acid anhydrides is moderate but faster than that of traditional cyclohexane epoxide-type resins and slower than that of the glycidyl ester-type resins. This reactivity was also examined using model compounds. The heat deflection temperature of the hexahydro-phthalic anhydride-cured resins is shown to be directly proportional to the number of epoxy groups in the molecules. The flexural strength of the cured resins is nearly equivalent to that of the commercial resins, although the flexural elongation of the resins is larger than that of the rigid cyclohexane epoxide-type resins. The thermal stability of the cured resins is comparable to typical rigid cycloaliphatic resins; furthermore, high water resistance of the cured resins is suggested to be attributed to the hydrophobic character of the C₈ chain by cross-linking. © 1993 John Wiley & Sons, Inc.     

High‐performance epoxy hybrid nanocomposites containing organophilic layered silicates and compatibilized liquid rubber

A mixture of two epoxy resins, tetraglycidyl 4,4′‐diaminodiphenyl methane and bisphenol‐A diglycidylether, cured with 4,4′‐diaminodiphenyl sulfone, was used as matrix material for high‐performance epoxy hybrid nanocomposites containing organophilicly modified synthetic fluorohectorite and compatibilized liquid six‐arm star poly(propylene oxide‐block‐ethylene oxide) (abbreviated as PPO). The hydroxy end groups of the poly(propylene oxide‐block‐ethylene oxide) were modified, yielding a six‐arm star PPO with an average of two pendant stearate chains, two phenol groups, and two hydroxy end groups. The alkyl chains of the stearate end groups played an important role in tailoring the polarity of the polymer. Its phenol end groups ensured covalent bonding between liquid polymer and epoxy resin. Two different organophilic fluorohectorites were used in combination with the functionalized PPO. The morphology of the materials was examined by transmission electron microscopy. The hybrid nanocomposites were composed of intercalated clay particles as well as separated PPO spheres in the epoxy matrix. As determined by dynamic mechanical analysis, the prepared composites possessed glass‐transition temperatures around 220°C. Although the tensile moduli remain unaltered, the tensile strengths of the hybrid materials were significantly improved. The relatively high fracture toughness of the neat resin, though, was not preserved for the hybrid resins. Scanning electron microscopy of the fracture surfaces revealed extensive matrix shear yielding for the neat resin, whereas the predominant fracture mode of the hybrid nanocomposites was crack bifurcation and branching. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3088–3096, 2004     

Hydrogen bonding in epoxy resin/poly(ϵ-caprolactone) blends

Poly(?-caprolactone) (PCL) of ca. 20,000 molecular weight is shown to be partially miscible with three aromatic-amine-cured epoxy resins. This conclusion is based on the depression of the epoxy T_g, the effect on physical and mechanical properties, and the observation that a large proportion (40-55%) of the PCL ester groups are involved in hydrogen bonding. This miscibility behavior is compared to PCL blends with anhydride-cured epoxy resins, which appear to have a two-phase morphology. The different miscibilities are rationalized on the basis of the existence of functional groups (e. g., hydroxyl) in amine-cured epoxies which are capable of hydrogen bonding to the PCL ester groups. Anhydride-cured epoxy resins contain fewer potential hydrogen bonding sites.     

Properties and processing characteristics of dielectric-filled epoxy resins

A family of casting composites, epoxy resins with mineral fillers, having a range of electrical properties, are being developed. In such composites, the dielectric constant is controlled primarily by varying the filler material in composition and proportions. The present work reports on the mechanical properties of composites made with two types of filler, an alumina powder (XA3500 from ALCOA) and a BaTiO₃/TiO₂ ceramic powder (ATD-50 from Ampex). Dependence of mechanical properties on curing agents was also determined. Filler contents from 0 to 40 percent volume were used. Epoxy systems contained single epoxy resin with both amine and anhydride hardeners. Processing of the anhydride-cured systems was easier than that of the amine-based systems because of their lower viscosity and longer gel time of the former. However, the anhydride-cured systems required higher processing temperatures. Curing kinetics and molecular bonding were investigated using a combination of differential scanning calorimetry, dynamic mechanical thermal analysis, and scanning electron microscopy. Activation energies of 11.2 kcal/mole and 12.1 kcal/mole were obtained for the curing of the amine-based and the anhydride-based composites respectively, and a small difference in the glass transition temperature was also observed. These effects can be attributed to the difference in the structure of the curing agents. The epoxy resin cured with NMA is less ductile compared with those cured with MTHPA or MHHPA due to slight chemical modification on the ring structures. This dependence of ductility on curing agent was observed in specimens with different filler contents. Although the presence of the filler materials was found to enhance the mechanical properties of the epoxy, the fracture mode in these materials is still brittle.     

环氧树脂改性超支化聚酯的合成及性能

以偏苯三酸酐、环氧氯丙烷及甲基丙烯酸缩水甘油酯为原料合成了超支化聚酯(HBP),再通过超支化聚合物的羧基与环氧树脂环氧基的反应得到环氧改性超支化聚合物;用GPC1、H-NMR、DSC、TGA表征了环氧改性超支化聚合物的结构和热性能;比较了不同环氧树脂用量改性前后树脂的光反应活性以及光固化涂层的耐擦洗性和硬度,测定了凝胶率-曝光时间曲线;以环氧改性超支化聚合物配制了光刻胶,在混合光源以及接触曝光的条件下,分辨率达到2~3μm,且图像十分清晰,断面整齐。环氧树脂用量为HBP羧基物质量的70%左右时,改性的超支化聚酯的光固化活性有明显提高,力学性能得到明显改进。     

Internal stress control in epoxy resins and their composites by material and process tailoring

The development of internal stress during cure of epoxy and hyperbranched polymer-modified epoxy resins was characterized, taking into account the evolving viscoelastic properties, the volumetric shrinkage due to the chemical reaction, and the thermal expansion. A criterion for void formation during cure in a constrained mold was proposed, providing guidelines for the construction of a process window for manufacturing of void-free composites. It was shown that the internal stress development in epoxy resins during cure is strongly influenced by the presence of hyperbranched polymer modifiers. The role of these modifiers was illustrated for the case of autoclave processing of glass fiber/epoxy composites. This study showed that higher fiber volume fractions could be used with hyperbranched polymer-modified resins than with unmodified resins, for producing void-free laminates. It also appeared that by suitable tailoring of the process cycle, a fully stress-free laminate could be obtained after cure, using the modified resin.     

Effects of cross-linked networks on dielectric properties of epoxy resins based on molecular dynamics

In this paper, three epoxy resin systems commonly used in power equipment are prepared to obtain cross-linked networks with structural differences. The relationship between microscopic structures and dielectric properties of epoxy resins is investigated and discussed. Experimental results show that the polarization and conductance losses are inhibited in the anhydride-cured systems with methyl groups. The molecular dynamics (MD) simulation shows that rigid anhydride structures (such as methyl groups) play a major role in reducing the local segment mobility and increasing the free volume at cross-linking points. The decrease in local segment mobility has been confirmed by the decrease of mean square displacement (MSD) at the cross-linking points, which is consistent with the change of measured polarization and conductance loss. In the glassy state, the dielectric properties of different anhydride-cured systems can be reflected by local MSD at the cross-linking points. At high temperatures near the glass transition temperature, both the free volume and network mobility increase significantly, which reflects the increased dielectric relaxation strength and conductance loss. The understanding of the structure–property relationships could provide a theoretical foundation for epoxy modification in a controlled manner for power equipment applications.     

Perspectives of Epoxy/Graphene Oxide Composite: Significant Features and Technical Applications

In this article, advancement in epoxy/graphene oxide composites is presented. These materials are comprised of graphene oxide (GO) as filler (carbon-based material, thermodynamically stable, two-dimensional, planar and layered structure). Due to improved properties (mechanical response, low density, electrical resistance, and thermal stability), epoxy resins are used in several applications. Graphene oxide proposes unique properties to epoxy composites as high surface area, thermal and electrical conductivity as well as mechanical and barrier properties, relative to neat matrix. The corresponding significance of epoxy/GO-based materials, related challenges, and potential exploitation regarding technical applications (aerospace, gas sensor, electronic devices, etc.) have been overviewed.     

超支化聚合物在环氧树脂中的应用

综述了超支化聚合物在环氧树脂中的应用,简述了超支化环氧树脂、超支化环氧树脂固化剂和超支化环氧树脂添加剂的合成及应用进展,展望了其研究前景。     

Synthesis of epoxy‐functionalized hyperbranched poly(phenylene oxide) and its modification of cyanate ester resin

High curing temperature is the key drawback of present heat resistant thermosetting resins. A novel epoxy‐functionalized hyperbranched poly(phenylene oxide), coded as eHBPPO, was synthesized, and used to modify 2,2′‐bis (4‐cyanatophenyl) isopropylidene (CE). Compared with CE, CE/eHBPPO system has significantly decreased curing temperature owing to the different curing mechanism. Based on this results, cured CE/eHBPPO resins without postcuring process, and cured CE resin postcured at 230°C were prepared, their dynamic mechanical and dielectric properties were systematically investigated. Results show that cured CE/eHBPPO resins not only have excellent stability in dielectric properties over a wide frequency range (1–10⁹Hz), but also show attractively lower dielectric constant and loss than CE resin. In addition, cured CE/eHBPPO resins also have high glass transition temperature and storage moduli in glassy state. These attractive integrated performance of CE/eHBPPO suggest a new method to develop high performance resins. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Quaternary phosphonium compounds as latent accelerators for anhydride-cured epoxy resins. I. Latency and cure characteristics

Quaternary phosphonium compounds have been found to be extremely effective latent accelerators for anhydride-cured bisphenol A epoxy resins; at concentrations from 0.01% to 0.25%, fast gel times are found in the temperature range of 135°–200°C combined with very good storage properties at ambient temperatures. Using these materials as accelerators, it is possible to formulate long-life, one-component epoxy resins. From gel time data, Arrhenius plots were made for some of these phosphonium compounds, and results indicate low activation energy values of the order of 16.1 kcal/mole. Reaction mechanisms are proposed to explain the effectiveness of these phosphonium compounds as latent accelerators. The initiation mechanism probably involves the formation of hydrogen-bonded phosphonium–epoxy or phosphonium–anhydride complexes which rearrange on the application of heat to form activated species resulting in polymerization of the epoxy–anhydride components. The transfer of a proton from the phosphonium complex(es) to other epoxy or anhydride molecules would appear to be the rate-determining step in this initiation mechanism. Comparison of other well-known accelerators used for the anhydride cure of bisphenol A epoxy resins shows quaternary phosphonium compounds to be among the most effective accelerators disclosed to date.     

Physical and mechanical properties of dental nanocomposites composed of aliphatic epoxy resin and epoxidized aromatic hyperbranched polymers

Aliphatic epoxy resin (UVR6105) and epoxidized aromatic hyperbranched polymers (HBP) were used as dental resin matrixes, siliane‐treated inorganic nanoparticles as inorganic fillers, ethyl 4‐dimethylaminobenzoate, camphorquinone, and 4‐[(2‐hydroxytetradecyl)oxy] phenyl‐phenyliodoniumhexafluoroantimonate (CD1012) as initiators to formulate new kinds of dental nanocomposites. Their physical and mechanical properties were tested and the inner structure was observed by using scanning electron microscope (SEM) and transmission electron microscope (TEM), respectively. The 7 series thermal analysis system was used to determine the glass transition temperature of dental resins. Compressive strengths of dental nanocomposites are lower, diametral tensile strengths are comparable with, flexural strengths are higher than those of commercial hybrid composite (Spectrum‐TPH). The addition of HBP decreased the glass transition temperature of aliphatic epoxy resin. SEM photo micrograph shows that the nanoparticles were well dispersed and inlayed in the resin matrixes. TEM photo micrograph shows that the inner structure of dental resins presents club‐shaped. Epoxidized aromatic hyperbranched polymer can strengthen and toughen aliphatic epoxy resin. These nanocomposites are potential for dental application. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Influence of hydroxyl functionalized hyperbranched polymers on the thermomechanical and morphological properties of epoxy resins

Rheological, thermomechanical, and morphological properties of blends of two different epoxy resins with hydroxyl functionalized hyperbranched polymers have been studied. The hydroxyl functionalized hyperbranched polymers used in this work had different generation number and different number of terminal groups. The difunctional epoxy resin has been also mixed with a linear aromatic thermoplastic in order to compare its effects with that of the hyperbranched polymers. All the blends have been characterized by linear elastic fracture mechanics (LEFM) testing to evaluate the efficiency of the two types of toughening modifiers. In addition, the water uptake has been evaluated for all the formulations. POLYM. ENG. SCI. 45:225–237, 2005. © 2005 Society of Plastics Engineers     

Role of non-functionalized oxide nanoparticles on mechanical properties and toughening mechanisms of epoxy nanocomposites

Over the past few decades, the use of epoxy resins has gained significant attention from worldwide researchers due to its advantages in structural applications in various sectors like automotive, construction, and aerospace industries. This article summarizes and reviews the research on mechanical properties and toughening mechanism of epoxy composites filled with non-functionalized oxide nanoparticles. The incorporation of nanomaterials into the polymer matrix has been considered to be the most effective route to improve the mechanical properties of polymer composites. But the inherent brittle nature and cross-linking ability of epoxy makes it vulnerable to crack initiation and crack growth and limits its use in advanced structural applications. Recently, various kinds of nanofillers such as carbon nanotubes (CNTs), organic and inorganic oxide nanoparticles have attracted industrial interest due to their excellent mechanical, thermal, and electrical properties which can provide a dramatic improvement in the properties of epoxy composites but their dispersion issue, agglomeration and bundling problems deteriorate several important mechanical parameters of the epoxy composites. To date, no review article focused on the role of non-functionalized oxide nanoparticles on the improvement in mechanical properties of the reinforced epoxy composites. This review article assesses and summarizes some most recent findings on the de-agglomeration process, mechanical properties, and toughening mechanisms of epoxy nanocomposites reinforced with four types of most preferred non-functionalized oxide nanoparticles such as Al₂O₃, TiO₂, SiO_2, and ZrO₂.     

不同POSS对磷⁃硅协同阻燃环氧树脂性能的影响

将两种多面体低聚倍半硅氧烷(POSS)分别与9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)基有机磷阻燃剂(D-bp)复配,制备了磷-硅协同阻燃环氧树脂,并对其阻燃、热、力学和动态力学性能等进行分析.结果表明,在磷含量仅为0.25％(质量分数,下同)时,磷-硅协同阻燃环氧树脂就能达到UL 94 V-0级...     

超支化聚酯在环氧树脂改性中的研究进展

综述了超支化聚酯(HBPE)在环氧树脂改性中的研究进展,首先对端羟基/端羧基/端环氧/端氨基HBPE的制备方法进行了总结;随后对不同端基的HBPE在环氧树脂的增韧改性及其增韧机理的研究进展进行了介绍;然后介绍了不同端基的HBPE对环氧树脂固化性能的影响研究.最后分析了HBPE在环氧树脂改性领域中需要关注的问题,指出未来...     

Radiation curing of hyperbranched polyester resins

A research area that has obtained increasing interest during the last decade concerns improvement of macromolecular properties by changes in the macromolecular architecture. One group of these materials is dendritic polymers, which are highly branched structures exhibiting very different properties compared with linear polymers. One potential application for these polymers is as radiation curable thermoset resins. This article describes a study where the use of an aliphatic hyperbranched polyester as a base for new radiation curable thermoset resins. The hyperbranched polyesters have been characterized with respect to cure rate and final mechanical properties compared with conventional resins. It is shown that hyperbranched polyesters can be used as versatile scaffolds for various radiation curable resin structures. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 612–618, 2000     

Novel moisture-cured hyperbranched urethane alkyd resin for coating application

A hyperbranched polyol (HBP) was synthesized using dipentaerythritol as a core material and 2,2-bis(methylol) propionic acid as a chain extender. This was reacted with varying concentrations of soya fatty acid to make hyperbranched alkyd (HBA) resins. The HBA resins containing unreacted hydroxyl groups were reacted with isophorone diisocyanate at NCO/OH ratio of 1.6:1 to make high solid hyperbranched urethane alkyd (HBUA) resins. The excess NCO content in the HBUA resins was used to cure with atmospheric moisture, and thus moisture-cured HBUA coatings were formed. The resins were characterized by FTIR, and ¹³C NMR spectroscopic analysis. A series of such resins were made using different fatty acid/isocyanate ratios with respect to the hydroxyl groups present in the HBP. The effect of compositions on the mechanical and weathering properties of the cured resins was investigated. It was observed that there was an optimum fatty acid–isocyanate ratio in terms of the requirements of solvent, mechanical and weathering properties of the resin. The requirement of solvents for formulating HBUA coatings is much lower compared to linear alkyd-based coatings. The present study reveals that the moisture-cured HBUA resins can be used as a binder material in the field of low-pollution weather-resistance coatings.