Studies on UV‐stable silicone–epoxy resins

Silicone–epoxy resins were synthesized through hydrosilylation of 1,2‐epoxy‐4‐vinyl‐cyclohexane with 1,3,5,7‐tetramethycyclotetrasiloxane. The silicone–epoxy resins showed high reactivity in the presence of aluminum complex/silanol compound catalysts. Curing of the resins was effected at extremely low concentrations of the aluminum acetylacetonate/Ph₂Si(OH)₂ catalyst to give hard materials with optical clarity. For the silicone–epoxy resins containing Si? H bonds, Al(acac)₃ alone is effective for the curing. The cured silicone–epoxy resins showed excellent UV resistance. An improvement in the lifetime of UV‐LEDs was achieved using the silicone–epoxy compositions as encapsulant. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3954–3959, 2007     

Preparation and characterization of silicone resin nanocomposite containing CdSe/ZnS quantum dots

We report the preparation of the core/shell cadmium selenide/Zinc sulfide quantum dots (CdSe/ZnS QDs)‐silicone resin nanocomposite through the solution‐mixing method, followed by thermal hydrosilylation. After dispersing QDs into Dow Corning two‐component silicone resins (OE6630A and OE6630B at 1:4 mixing ratio by weight), the resins were cured at 150°C for 1.5 h to produce QD‐silicone resin nanocomposites. The curing behavior of the silicone resins resulting from the thermal hydrosilylation was studied using differential scanning calorimetry (DSC). The properties of the QD‐silicone resin nanocomposites were investigated by ultraviolet–visible (UV–vis), fluorescence, confocal laser scanning microscopy (CLSM), atomic force microscopy (AFM), and thermogravimetric analysis (TGA) measurements. The QDs that contain trioctylamine (TOA) as the original ligand can poison the Pt catalyst in the resins and inhibit the curing process by increasing the exothermic peak temperature, at which a lower heat of hydrosilylation is observed. Incorporating a small amount of CdSe/ZnS QDs (0.1 wt%) can greatly improve the thermal stability of the silicone resins. Moreover, CdSe/ZnS QDs tend to form clusters that are relatively homogeneously distributed in a cured silicone resin, offering good optical properties of 11.2 lm W⁻¹ luminous efficiency and 14.6% photoluminescence conversion efficiency (PCE) in light emitting device (LED) test. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Facile strategy and mechanism of greatly toughening epoxy resin using polyethersulfone through controlling phase separation with microwave-assisted thermal curing technique

Toughening has been the essential issue for developing high-performance thermosetting resins. Herein, starting from polyethersulfone (PES) and bisphenol A epoxy resin (EP), a facile strategy is developed to prepare tough resins through controlling phase structure with microwave-assisted thermal curing. PES/EP resins cured with the assistance of microwave curing (m-PES/EP) have two major differences compared with those using traditional heat curing (t-PES/EP), one is high degree of phase separation, and the other is phase separation mechanism. Initial phase separation of all t-PES/EP resins follows spinodal decomposition mechanism, while those of m-PES/EP systems with 8 wt% and 18 wt% of PES follow nucleation and growth mechanism. These differences are derived from the fact that microwave curing has much faster phase separation rate and curing reaction rate than thermal curing owing to the higher thermal effect. Differences in phase structure bring different macro performances, and m-PES/EP systems have higher impact strengths, fracture toughnesses, and flexural strengths than t-PES/EP resins. This investigation provides a facial and effective way of developing higher performance thermoplastic/thermosetting resin system through controlling phase structure. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48394.     

Effects of silicone resins on copolymerization of acrylated epoxidized soybean oil

In this work, effects of the silicone resins on copolymerization of the acrylated epoxidized soybean oil were investigated. Rheological characteristics, curing behaviors, and thermal properties of acrylate epoxy soybean oil prepolymer (AP), silicone prepolymer (SP), and their hybrids (AP/SP) were studied in detail. Spots in a snowflake pattern were observed on the fracture section surface of cured AP/SP hybrid resins by SEM. According to the change of polymer groups revealed by Fourier transform infrared, a possible reaction between AP and SP was proposed. The curing mechanism of AP/SP hybrids was researched, which was suggested to be an autocatalytic curing process. Furthermore, the degree of cure, the activation energy (E_α) and the reaction frequency factor (A) of the curing reaction were estimated. It was found that the cure kinetic of AP/SP hybrid resins could be well-described by a Sesthk-Bergglen model with the numerical optimization based on the Kissinger method and the Malek approach. The experimental results show that the mass retention rates of AP/SP hybrid resins were significantly increased after curing, indicating that the thermal stability of AP was enhanced with the addition of SP.     

含钛有机硅树脂改性端羟基饱和聚酯的合成及性能

通过缩聚反应,用含钛有机硅预聚体对端羟基饱和聚酯树脂进行化学改性,用傅里叶变换红外光谱对改性聚酯树脂的结构进行了表征.以封闭型聚异氰酸酯为固化剂将其固化成膜,检测了涂膜的物理机械性能、耐热性以及耐蚀性.结果表明,改性后的聚酯具有良好的物理机械性能,按质量比1:1改性后的聚酯树脂其耐热、耐蚀性能显著提高,开始分解温度从改...     

耐热性汽车制动材料的研究

围绕耐热性汽车制动材料的研制，用索氏抽提法测定了双酚Ａ型苯并恶嗪中间体在路易斯酸和六次甲基四胺作用下树脂的固化程度，同时利用ＩＲ、ＤＴＡ、ＴＧＡ等测试方法研究了固化物的结构和热稳定性。制备了以该树脂为基体的制动材料，测定了制动材料的热膨胀性及摩擦磨损性能，结果表明，开环聚合酚醛树脂具有良好的热稳定性，其制动材料高温摩擦系数稳定，热恢复性良好，热膨胀小。     

Synthesis,thermal properties,and flame retardance of the epoxy‐silsesquioxane hybrid resins

Epoxy/silsesquioxane‐OH (EP‐SDOH, ED) hybrid resins were prepared from cyclohexyl‐disilanol silsesquioxane (SDOH) and diglycidyl ether of bisphenol A via the reaction between silanol and the oxirane group, with the cobalt naphthanate as a catalyst. It was found that incorporation of SDOH allows the reaction between oxirane ring and Si? OH, and the silsesquioxane cage structure can be the main chain or as the side chain of the hybrid resin. The EP‐SDOH hybrid resins with various SDOH contents were cured by 4,4′‐diaminodiphenylsulphone, and the curing reaction was investigated by differential scanning calorimetry. The curing characteristics of EP‐SDOH hybrids had been observed to be influenced by the content of SDOH in the hybrid. The differential scanning calorimetry thermograms indicated that the EP‐SDOH hybrid exhibited a higher initial temperature, peak temperature, as well as final temperature than those of the pure epoxy resin when cured by the same curing agent 4,4′‐diaminodiphenylsulphone. The curing kinetic parameters were calculated by using the Ozawa method and the results indicated that EP‐SDOH hybrids possess the same curing mechanism as the pure epoxy resin. The properties of the cured EP‐SDOH hybrid resins such as the glass transition temperature (T_g), dynamic mechanical analysis, thermal stability, as well as the flame retardance were also investigated, and the results showed that introducing silsesquioxane‐OH unit into epoxy resin successfully modified the local structure, made the chain stiffness, restrict the chain mobility, and eventually improved thermal stability and flame retardance of epoxy resin. POLYM. ENG. SCI., 47:225–234, 2007. © 2007 Society of Plastics Engineers.     

Behavior of nonazeotropic compositions of a styrene–unsaturated polyester resin analyzed through FTIR spectroscopy and dynamic mechanical thermal analysis

Styrene is one of the comonomers most frequently used in the curing of unsaturated polyester resins. The use of nonazeotropic compositions leads to the formation of networks, in which the styrene–polyester ratio varies significantly during curing, as shown through FTIR spectroscopy. Dynamic mechanical thermal analysis (DMTA) showed how the variation in the styrene content affects the network structure that is formed. The results showed a decrease in network density in the systems in which the azeotropic composition was not used. The styrene content is therefore a factor that governs the curing process, in addition to the ultimate properties of the cured resins. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3618–3625, 2003     

缩合型室温硫化硅橡胶耐热性的研究进展

从硅橡胶的分子结构分析了其耐热性优于普通橡胶的原因及热老化机理，并比较了几种硫化体系的缩合型室温硫化硅橡胶的耐热性，着重介绍了国内外提高室温硫化硅橡胶耐热性的方法和研究进展。     

聚苯基甲氧基硅氧烷改性环氧树脂的阻燃性能研究

采用氧指数(LOI),UL-94,热失重(TGA)等手段考察了聚苯基甲氧基硅氧烷(PPMS)改性对环氧树脂(E-20)固化体系阻燃性能的影响.相比未改性环氧体系,当m(E-20)∶m(PPMS)=73∶时,改性环氧体系的LOI由纯E-20环氧树脂的17.5%上升到21.5%;水平火蔓延速率由36.23 mm/min降低到26.60 mm/min;质量损失为5%时的热分解温度由134.7℃上升到163.0℃,750℃时残炭量由0.21%增加到25.79%.此外,还通过红外光谱对燃烧后的残炭结构进行了分析,探讨了相关阻燃机理.     

Synthesis and characterization of diphenylsilanediol modified epoxy resin and curing agent

A series of diphenylsilanediol modified epoxy resins and novel curing agents were synthesized. The modified epoxy resins were cured with regular curing agent diethylenetriamine (DETA); the curing agents were applied to cure unmodified diglycidyl ether of bisphenol A epoxy resin (DGEBA). The heat resistance, mechanical property, and toughness of all the curing products were investigated. The results showed that the application of modified resin and newly synthesized curing agents leads to curing products with lower thermal decomposition rate and only slightly decreased glass transition temperature (T_g), as well as improved tensile modulus and tensile strength. In particular, products cured with newly synthesized curing agents showed higher corresponding temperature to the maximum thermal decomposition rate, comparing with products of DGEBA cured by DETA. Scanning electron microscopy micro images proved that a ductile fracture happened on the cross sections of curing products obtained from modified epoxy resins and newly synthesized curing agents, indicating an effective toughening effect of silicon–oxygen bond.     

Study of high thermal conductive epoxy resins containing controlled high‐order structures

Heat is transported by phonons through dielectric solids such as ceramics and organic insulating resins. Especially in organic insulating resins, phonons scatter intensely mainly by their amorphous structure, which affects their thermal conductivities, usually 1 to 3 orders lower than those of ceramics and metals. Here, we show that by the thermosetting resin system with a crystal‐like structure that is microscopic anisotropy, the thermal conductivities of the resin themselves can be improved while keeping their macroscopic isotropy. We studied four kinds of diepoxy monomers with a biphenyl group or two phenyl benzoate groups as mesogens, and cured them thermally with an aromatic diamine curing agent. These thermal conductivities were maximally 5 times higher than that of conventional epoxy resins because mesogens were highly ordered to form crystal‐like structures to suppress phonon scattering. We also succeeded in the direct confirmation of the existence of crystal‐like structures in the epoxy resins by TEM observation. These results suggest a novel strategy to improve thermal conductivities of insulating resins themselves by controlling the high‐order structures. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2464–2467, 2003     

Comparison of microwave and thermal cure of epoxy–anhydride resins: Mechanical properties and dynamic characteristics

The objective of this work was to compare the mechanical properties of epoxy resins cured by thermal heating and microwave heating. Epoxy–anhydride (100:80) resins were cured in a domestic microwave oven and in a thermal oven. The hardening agents included methyl tetrahydrophthalic anhydride and methyl hexahydrophthalic anhydride. Three types of accelerators were employed. Thermal curing was performed at 150°C for 20 and 14 min for resins containing 1 and 4% accelerator, respectively. Microwave curing was carried out at a low power (207 or 276 W) for 10, 14, and 20 min. All cured resins were investigated with respect to their tensile properties, notched Izod impact resistance, and flexural properties (three‐point bending) according to ASTM standards. The tan δ and activation energy values were investigated with dynamic mechanical thermal analysis, and the extent of conversion was determined with differential scanning calorimetry. The differences in the mechanical properties of the thermally cured and microwave‐cured samples depended on the resin formulation and properties. Equivalent or better mechanical properties were obtained by microwave curing, in comparison with those obtained by thermal curing. Microwave curing also provided a shorter cure time and an equivalent degree of conversion. The glass‐transition temperatures (tan δ) of the thermally and microwave‐cured resins were comparable, and their activation energies were in the range of 327–521 kJ/mol. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1442–1461, 2005     

Synthesis and modification of trifunctional epoxy resin with amine terminated polydimethyl siloxanes for semiconductor encapsulation application

Epoxy resins based on the triglycidyl ether of tris(hydroxyphenyl)methane (TETM) possess a very high heat distortion temperature and superior thermal oxidative stability over other types of epoxy resins. The high performance trifunctional epoxy resin (TETM) was synthesized by the condensation of a hydroxybenzaldehyde with phenol followed by epoxidation with a halohydrin. The structure of the synthesized TETM was confirmed by infrared (IR), mass spectra (MS), and nuclear magnetic resonance (NMR) spectroscopy. Amine terminated polydimethylsiloxanes (ATPDMS) were used to reduce the stress of trifunctional epoxy resin cured with phenolic novolac resin for electronic encapsulation applications. The dispersed silicone rubbers effectively reduce the stress of cured epoxy resins by reducing the coefficient of thermal expansion (CTE) and flexural modulus, while the glass transition temperature (T_g) is depressed by only a small amount.     

电子束固化木器清漆的制备及性能研究

电子束（ EB）固化技术作为一种重要的辐射固化技术,其固化的清漆涂层性能在许多方面优于紫外（ UV）光固化清漆涂层。本研究通过选取不同类型的商品化丙烯酸树脂及活性稀释剂配制木器涂料配方,分别利用电子束（ EB）和紫外光（ UV）对其进行固化,然后对固化后的涂层进行基本性能、热性能和机械性能的表征。研究结果表明： EB固化速度快,固化膜具有较高的铅笔硬度和附着力,而且树脂种类和单体结构的不同会对电子束固化涂层的热性能及机械性能产生影响。     

Curing reaction of molybdenum–phenolic resins

The curing behavior and curing reaction kinetics of novel molybdenum–phenolic resins were studied with differential scanning calorimetry and thermogravimetry methods, the thermal degradation properties of the cured products were studied with thermogravimetry, and the mechanism of the curing reaction was investigated with Fourier transform infrared. When the mixing ratio of the molybdenum–phenolic resin (with 12% molybdenum) to the curing agent was 100/10 (w/w), the curing temperature and activation energy were at a minimum, the thermal degradation stability of the cured product was optimal, and the temperature corresponding to the maximum extent of curing was 200°C. The curing mechanism was similar to that of conventional phenolic systems. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1410–1415, 2003     

Preparation and characterization of biscyanamide resins containing o-substituted groups or phenyl–ether linkage

New biscyanamides containing o-substituted groups or a phenyl-ether linkage were synthesized. The curing reaction behaviors of the biscyanamides were investigated. All the prepared biscyanamides began to polymerize as soon as they melted after being put on a heated plate beyond a certain temperature. The cured resins of each biscyanamides were prepared on the optimal conditions. Optimal conditions for cured resins were obtained from the curing reaction behaviors of each biscyanamide by differential scanning calorimetry (DSC). The effect of chemical structures of the biscyanamides on the thermal and mechanical properties of the cured resins such as seen by thermal gravimetric analysis (TGA), density, and flexural strength were studied. The introduction of alkyl groups into the ortho position decreased intermolecular interactions. The introduction of a long phenyl-ether linkage into the structure gave a broad exothermal peak in the DSC and good workability for the preparation of the cured resins. Moreover, the extension between cross-linkings improved the flexibility of the cured resins. The cured resins with fluorine-containing substituent groups also had better thermal stability in the air compared with hydrocarbon group resins.     

Curing Characteristics and Thermal Properties of Epoxidized Soybean Oil Based Thermosetting Resin

Epoxidized soybean oil (ESO) was thermally cured using methylhexahydrophthalic anhydride (MHHPA) curing agent in the presence of 2-ethyl-4-methylimidazole (EMI) catalyst. The curing characteristics of ESO/MHHPA/EMI systems were characterized using Fourier transform infrared spectroscopy (FTIR), a dynamic mechanical analyzer (DMA) and a differential scanning calorimeter (DSC). FTIR spectra showed that the polyesterification rate in ESO/MHHPA/EMI systems increased with increasing of the catalyst concentration. DSC thermograms indicated that EMI-catalyzed ESO/MHHPA systems experienced enthalpy relaxation at low EMI concentration whereas the extent decreased with increasing of the EMI concentration. There is a direct relationship between the degree of conversion and crosslink density of the thermal cured ESO/MHHPA/EMI systems with EMI concentration. The curing characteristics of thermal curable ESO thermosetting resins were found to have influence on the thermal properties of the ESO systems. It was determined that the glass transition temperature (T _g) and storage modulus (E′) of cured ESO increased with increasing the EMI concentration whereas the damping properties of the ESO/MHHPA/EMI systems exhibited the reverse trend. It was found that the thermally curable ESO thermosetting resins experienced a two-stage thermal decomposition process.     

热固性树脂微波固化研究进展

综述了近年来热固性树脂及其复合材料的微波固化研究进展,重点讨论了热固性树脂微波固化与加热固化的比较,热固性树脂微波固化工艺,颗粒、纤维增强树脂基复合材料的微波固化研究。研究发现微波固化和热固化在本质上是相同的,然而,微波极大地加速了固化进程,对体系性能无损害;加入无机、金属填料以及纤维可以改变体系介电性能,控制微波工艺对材料进行精加工。最后介绍了微波热效应原理,并展望了微波热固化技术发展与应用。     

Novel phosphorilated flame retardant thermosets: epoxy-benzoxazine-novolac systems

Modified novolac resins with benzoxazine rings were prepared and cured with isobutyl bis(glycidylpropylether) phosphine oxide (IHPOGly) as crosslinking agent. Their curing behaviour using different epoxy/phenol molar ratios and with or without triphenylphosphine as catalyst was studied. Two different phenolic groups react with oxirane ring, those initially free and those generated after benzoxazine ring opening. In absence of catalyst, it is not possible to distinguish between them. However, for the catalyzed curing of the highest modification degree benzoxazine based novolac resin is possible to distinguish both reactions. The thermal, thermomechanical and flame retardant properties of the cured materials were measured. V-O materials were obtained when the resins were tested for ignition resistance with the UL-94 test.