Low-stress encapsulants by vinylsiloxane modification

Dispersed silicone rubbers were used to reduce the stress of cresol–formaldehyde novolac epoxy resin cured with phenolic novolac resin for electronic encapsulation application. The effects of structure, molecular weight, and contents of the vinylsiloxane oligomer on reducing the stress of the encapsulant were investigated. Morphology and dynamic mechanical behavior of rubber-modified epoxy resins were also studied. The dispersed silicone rubbers effectively reduce the stress of cured epoxy resins by reducing flexural modulus and the coefficient of thermal expansion (CTE), whereas the glass transition temperature (T_g) was hardly depressed. Electronic devices encapsulated with the dispersed silicone rubber modified epoxy molding compounds have exhibited excellent resistance to the thermal shock cycling test and have resulted in an extended device use life. © 1994 John Wiley & Sons, Inc.     

Epoxidized natural rubber/epoxy blends: Phase morphology and thermomechanical properties

Epoxidized natural rubbers (ENRs) were prepared. ENRs with different concentrations of up to 20 wt % were used as modifiers for epoxy resin. The epoxy monomer was cured with nadic methyl anhydride as a hardener in the presence of N,N‐dimethyl benzyl amine as an accelerator. The addition of ENR to an anhydride hardener/epoxy monomer mixture gave rise to the formation of a phase‐separated structure consisting of rubber domains dispersed in the epoxy‐rich phase. The particle size increased with increasing ENR content. The phase separation was investigated by scanning electron microscopy and dynamic mechanical analysis. The viscoelastic behavior of the liquid‐rubber‐modified epoxy resin was also evaluated with dynamic mechanical analysis. The storage moduli, loss moduli, and tan δ values were determined for the blends of the epoxy resin with ENR. The effect of the addition of rubber on the glass‐transition temperature of the epoxy matrix was followed. The thermal stability of the ENR‐modified epoxy resin was studied with thermogravimetric analysis. Parameters such as the onset of degradation, maximum degradation temperature, and final degradation were not affected by the addition of ENR. The mechanical properties of the liquid‐natural‐rubber‐modified epoxy resin were measured in terms of the fracture toughness and impact strength. The maximum impact strength and fracture toughness were observed with 10 wt % ENR modified epoxy blends. Various toughening mechanisms responsible for the enhancement in toughness of the diglycidyl ether of the bisphenol A/ENR blends were investigated. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39906.     

Studies on The Modification of Epoxy Resin with Silicone Rubber

In order to find a compatibilizer for epoxy resin/silicone rubber systems, interfacial tension of epoxy resin mixed with modified silicone oils which had the compatible groups to epoxy resin was measured against RTV silicone rubber and silicone oil. From the results, it was found that one of polyether modified silicone oils (EtMPS) had strong interfacial activity. Then using the EtMPS as the compatibilizer, RTV silicone rubber or silicone diamine was filled in epoxy resin. The effects of silicone content of these materials on impact fracture energy and on peel strength were investigated. The impact fracture energy of epoxy resin was increased by the addition of RTV silicone rubber up to two times that of unmodified resin while silicone diamine had almost no effect which might be due to the small molecular weight. T-peel strengths of aluminium plates bonded by epoxy resin filled with RTV silicone rubber and with silicone diamine effectively increased with the increasing of silicone content showing the maximum at 10 ∼ 20 phr. The fracture surfaces after the mechanical tests of these materials were observed by a scanning electron microscope. Many particles of silicone rubber in the size of 1 ∼ 20 μ were observed over the fracture surface.     

Studies on The Modification of Epoxy Resin with Silicone Rubber

In order to find a compatibilizer for epoxy resin/silicone rubber systems, interfacial tension of epoxy resin mixed with modified silicone oils which had the compatible groups to epoxy resin was measured against RTV silicone rubber and silicone oil. From the results, it was found that one of polyether modified silicone oils (EtMPS) had strong interfacial activity. Then using the EtMPS as the compatibilizer, RTV silicone rubber or silicone diamine was filled in epoxy resin. The effects of silicone content of these materials on impact fracture energy and on peel strength were investigated. The impact fracture energy of epoxy resin was increased by the addition of RTV silicone rubber up to two times that of unmodified resin while silicone diamine had almost no effect which might be due to the small molecular weight. T-peel strengths of aluminium plates bonded by epoxy resin filled with RTV silicone rubber and with silicone diamine effectively increased with the increasing of silicone content showing the maximum at 10 ～ 20 phr. The fracture surfaces after the mechanical tests of these materials were observed by a scanning electron microscope. Many particles of silicone rubber in the size of 1 ～ 20 μ were observed over the fracture surface.     

低模量硫化硅橡胶粘接研究

采用sol—gel工艺自制的SiO2补强增韧环氧树脂作为胶粘剂,对低模量硫化硅橡胶与金属或复合材料进行粘接试验,分析胶粘剂中SiO2理论含量及粘接工艺对粘接性能的影响,并把硫化硅橡胶放在改性环氧树脂中进行溶张试验,探索胶粘剂对硅橡胶的粘接机理、结果表明,随着SiO2先驱体-有机硅烷含量的增加,硅橡胶的溶胀程度提高改性环氧树脂胶粘刺能浸入硅橡胶的表层,对硅橡胶具有良好的亲和力。用该胶粘剂对硅橡胶与金属或复合材料进行粘接时,取得了良好的粘接效果。     

The thermal stability investigation of microencapsulated ammonium polyphosphate/siloxane‐modified epoxy resin composites

In this investigation, epoxy resin composites containing phosphate and silicone were prepared from microencapsulated ammonium polyphosphate (MFAPP) and poly(methylphenyl siloxane) (PMPS). Silicone‐containing epoxy (E‐S) copolymers were gained by the grafting reaction between ? OCH₃ of PMPS and ? OH of E51. And, a fixed weight of MFAPP was introduced to epoxy systems via the physical blending method. The chemical structure of the E‐S copolymer was determined by Fourier transform infrared spectroscopy (FTIR) and ¹H‐NMR. The impact testing results revealed that the impact toughness was improved slightly. The thermogravimetric analysis (TGA) results demonstrated that the thermal degradation property in high temperature region and solid residue yield at 800 °C were enhanced remarkably with increasing PMPS content, whether the testing atmosphere was in nitrogen or oxygen. Moreover, an obvious synergistic effect of silicon and phosphorus on promoting the thermo‐oxidative degradation stability and solid residue at 800 °C was proved. Furthermore, the scanning electron microscope micrographs and FTIR result of residual charred crusts of EA‐S systems after the TGA testing in air manifested that the bubbled charred layer and silicon‐ and phosphorus‐containing residue took chief responsibility for thermo‐oxidative degradation property and solid residue yield. So the MFAPP/siloxane‐modified epoxy resin composites have a significant development prospect in high‐temperature resistant organic adhesives and coatings. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45272.     

Processing and characterization analysis of pyrolyzed oil rubber (from waste tires)‐epoxy polymer blend composite for lightweight structures and coatings applications

In this experimental investigation, the authors have fabricated and characterized composites made from pyrolysis oil rubber and epoxy resin. As the dumping of waste scrap tires poses a serious environmental threat, the pyrolysis oil rubber was extracted from these waste tires only. The prepared blend having pyrolysis oil with various weight percentages (wt%) was examined on the basis of various physical, microstructural, mechanical, and thermal tests. The microstructural tests (scanning electron microscopy and X‐ray diffraction) analysis complemented with the mechanical tests (tensile, compression, flexural, hardness, and impact) results and confirmed that the 4.4 wt% of pyrolysis oil in epoxy resin sample exhibited the best results in toughening of the polymer network. Furthermore, the thermal analysis (differential thermal analysis and thermogravimetric analysis), electrical conductivity, density, water absorption, gas chromatography–mass spectroscopy, and Fourier‐transform infrared tests for the composites were also performed. Low density and high tensile strength than neat epoxy resin makes this composite a potential candidate for fabricating lightweight structures and in polymer coatings for automotive industries. POLYM. ENG. SCI., 59:2041–2051, 2019. © 2019 Society of Plastics Engineers     

Quaternary phosphonium modified epoxidized natural rubber: effect of reaction time,reaction mechanism,thermal property and antimicrobial activity

Herein we endow epoxidized natural rubber with antimicrobial activity by chemical modification. The rubber is firstly ring-opened by bromoacetic acid and then modified by antimicrobial group quaternary phosphonium salt. Using the hydrogen nuclear magnetic resonance spectroscopy (¹H NMR) and the ICP atomic emission spectrometry (ICP-AES), the degree of epoxidation, the convert ratio of epoxy groups, and the phosphorus content of the products are measured, and then the effects of reaction time on the structure of products are investigated. The possible reaction mechanism and side reactions in ring-opening procedure are discussed through the comparison of data with different reaction time, and the ring-expansion reaction is supposed to be dominated in the side reactions. The thermal properties of modified rubbers and the structural factors behind are also investigated using differential scanning calorimeter and thermogravimetric analyzer. Antimicrobial activities of modified rubbers with different ring-opening reaction time toward Escherichia coli are studied, and the activity may increase with the content of quaternary phosphonium salt groups. This research may have the benefit for optimizing the structure of chemically modified antimicrobial rubbers.     

A new UV-curable PU resin obtained through a nonisocyanate process and used as a hydrophilic textile treatment

Oligo-fluorosiloxane (DFOS) and epoxy-containing oligo-fluorosiloxane (DFEHOS) were synthesized by the hydrolytic condensation reaction to modify 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate (ERL-4221) for potential application in LED packaging. The chemical structures of DFOS and DFEHOS were characterized by Fourier transform infrared (FT-IR), ²⁹Si nuclear magnetic resonance (²⁹Si NMR), and gel permeation chromatography (GPC). The thermal behavior, mechanical properties, morphologies of impact fracture surfaces, surface wettability and absorbency of the modified epoxy resins were examined by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), tensile and impact testing, scanning electron microscopy (SEM), and contact angle measurement, respectively. The experimental results indicated that the contact angles, surface energies and water absorption ratios of the modified epoxy resins were effectively improved by the introduction of oligo-fluorosiloxanes. Compared to neat epoxy resin, the thermal stabilities of DFEHOS-modified epoxy resins were basically kept, and that of DFOS-modified epoxy resins were slightly depressed with the increasing content of modifiers. As the additive quantity of modifiers was about 5pph to 15pph relative to ERL-4221, good thermal stability, fracture toughness and surface hydrophobicity of the modified epoxy resin was exhibited, and the cured DFEHOS-10 that embraced the relatively optimum comprehensive property was possible for LED encapsulation. Moreover, the reactable groups formed during hydrolytic condensation in DFOS and DFEHOS made good compatibilities between the modifiers and the epoxy matrix.     

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.     

Curing of epoxy/novolac system modified with reactive liquid rubber and carbon filler

The curing behaviour of epoxy resins modified with reactive liquid rubber, using a novolac resin as a hardner was studied by means of differential scanning calorimetry in isothermal (100, 130 and 150 °C) and non-isothermal conditions (2, 5, 10 and 15 °C min^-1). The influence of carboxyl- (CTBN) and epoxy- (ETBN) terminated butadiene-acrylonitrile copolymers on the kinetic parameters and glass transition temperature (T_g) of cured epoxy systems was determined. The effect of grinded bituminous coal as an organic filler into epoxy network was also investigated. The carboxyl-end groups strongly enhanced the curing rate, in contrast to the epoxy-terminated rubber (ETBN) that had only a minor effect on the curing reactions. The presence of coal accelerated curing in its early stage. The T_g of completely cured epoxy was practically unaffected by the presence of carbon filler and reactive rubbers and was equal about 132 °C. The apparent curing activation energies were determined. A smaller activation energy was observed only for CTBN/epoxy/novolac system. The effect of reactive rubber and coal on the Charpy impact resistance of cured epoxy systems was also discussed.     

Synthesis and modification of a trifunctional epoxy resin with amino-terminated poly(dimethylsiloxane)s for semiconductor encapsulation

A high-performance trifunctional epoxy resin based on the triglycidyl ether of tris (4-hydroxyphenyl)-methane (TETM) was synthesized by the condensation of 4-hydroxybenzaldehyde with phenol followed by epoxidation with epichlorohydrin. The structure of TETM was confirmed by mass spectra, infrared and nuclear magnetic resonance spectroscopy. Amino-terminated poly(dimethylsiloxane)s were used to reduce the stress of the trifunctional epoxy resin cured with phenolic novolac resin for electronic encapsulation application. The dispersed silicone rubbers effectively reduce the stress of cured epoxy resins by reducing the coefficient of thermal expansion and flexural modulus while the glass transition temperature was hardly depressed.     

纳米二氧化钛对MQ硅树脂增强硅橡胶性能的影响

以MQ硅树脂增强加成型硅橡胶为基体,采用机械共混方式,加入少量纳米二氧化钛进行改性,制备了纳米二氧化钛改性硅橡胶。试验结果表明,MQ硅树脂增强的硅橡胶中,加入少量纳米二氧化钛改性后,能够改善硅橡胶的力学性能,其硬度和断裂伸长变化不大,而拉伸强度和抗撕强度提高,硅橡胶的耐热性也提高。溶胀实验表明,添加纳米粒子后,硅橡胶的溶胀比降低,凝胶质量分数和交联密度增加。     

Effects of epoxy resin on mechanical and thermal characteristics of poly(propylene oxide)/poly(butyl acrylate) networks

We report mechanical and thermal characteristics of a network composed of poly(propylene oxide) (PPG) and poly(butyl acrylate) crosslinked with tolylene diisocyanate. It was found that addition of about 4 wt % of an epoxy resin resulted in a higher mechanical toughness and less discoloration. Furthermore, it was found that the epoxy has a self‐restoration function against thermal degradation of the network. The reaction mechanism between the network and the epoxy was investigated with infrared spectroscopy and ¹³C‐NMR and the effect of the epoxy resin on the thermal stability and physical properties is discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1886–1893, 2000     

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.     

Application of a new modified epoxy adhesive for bonding fluorine rubber to metal

Adhesion of fluorine rubber to metals is an important issue. The aim of this work was to develop a new kind of adhesive for bonding fluorine rubber to metals. A new modified epoxy adhesive containing a special tackifier resin obtained from polysulfones with a high heat deflection temperature (HDT) was prepared. Study on the curing behavior of the adhesive was carried out. Properties of the adhesive and the effects of several main factors were studied by gelation time test, differential scanning calorimetry (DSC) and Fourier transform infrared (FT-IR) spectroscopy. The optimum amount of the tackifier resin was found to be 50 phr; the average tensile lap shear strength could be achieved to a level of 8–10 MPa. Infrared attenuated total reflection (IRATR) spectroscopy indicated that the tackifier resin accelerated the establishment of epoxy resin adhesion to steel, and also promoted bonding and vulcanization of fluorine rubber. Easy diffusion of cyanamide (decomposition compound of dicyandiamide (DICY) in the curing process) into epoxy resin and fluorine rubber facilitated the dissolution and reaction of DICY, and also promoted formation of complex bond between fluorine rubber and adhesive, hence an enhanced adhesion of fluorine rubber to metal was achieved.     

Study of impact properties and morphology of 4,4′‐diaminodiphenyl methane cured epoxy resin toughened with acrylate‐based liquid rubbers

Randomized carboxyl poly(2‐ethylhexyl acrylate) (A‐1) and randomized epoxy poly(2‐ethylhexyl acrylate) (B‐1) rubbers were synthesized in the form of liquid rubber by a solution polymerization technique. The liquid rubbers A‐1 and B‐1 were characterized by ¹H NMR and IR spectroscopic analysis, non‐aqueous titration, viscosity measurements and gel permeation chromatography. The liquid rubbers A‐1 (M?_n = 3900 g mol^?1), B‐1 (M?_n = 4100 g mol^?1) and a (1:1) mixture of A‐1 and B‐1 were pre‐reacted with epoxy resin separately and the modified epoxy networks were made by curing with high temperature curing agent. The modified epoxy networks were evaluated by unnotched Izod impact testing. The morphology and toughening behaviour were analysed by scanning electron microscopy. Optimum properties were obtained with the mixture of A‐1 and B‐1. Copyright © 2003 Society of Chemical Industry     

Enhancement in electrical and thermal performance of high-temperature vulcanized silicone rubber composites for outdoor insulating applications

High-temperature vulcanized silicone rubber composites are highly desirable as outdoor insulating materials due to their immense thermal and electrical performance. The aim of this work is to study the role of co-combined fillers (modified fumed silica [MFS], titanium dioxide [TiO₂], with graphene [G]) on electrical and thermal properties of silicone rubber (S) composites. The dielectric response of S/MFS_10 phr and S/TiO₂_20 composites tailored with 2 phr G was characterized by broadband dielectric spectroscopy. The hybrid filler/composites were found to show higher thermal stability when 2 phr G was added. In addition, a low quantity of G filler was found to slightly increase the AC dielectric breakdown strength of the S/MFS_10 and S/TiO₂_20, where an improvement of 3 and 5% was found, respectively. Several steps were observed in the thermal decomposition of the S rubber composites by thermogravimetric analysis-Fourier-transform infrared spectroscopy. Our findings revealed great potentials for fabricating hybrid-filler/silicone rubber composites with enhanced electrical and thermal properties for outdoor insulating applications.     

Effect of copper oxides on the thermal oxidative degradation of the epoxy resin

The effect of copper oxides on the thermal oxidative degradation of a brominated epoxy resin–dicyandiamide system was studied using Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). The addition of small amounts of Cu₂O or CuO fillers to the epoxy resins affected the relative amounts of highly reacted cyclic species formed during thermal aging and induced catalytic degradation of the epoxy resins. The overall and initial activation energies of the degradation process were found to decrease, and the order in the degradation kinetics of the epoxy resin changed from a near zero order to negative domain (autocatalytic nature) in the presence of copper oxides. © 1994 John Wiley & Sons, Inc.     

The synthesis of a secondary branched epoxy-modified silicone resin and its application at low temperature

To enhance the fracture toughness of epoxy resin at low temperature, a secondary branched epoxy-terminated silicone resin (ESR-6) was synthesized and incorporated into bisphenol A epoxy resin at different contents. The structure of ESR-6 was characterized by Fourier transform infrared spectroscopy and nuclear magnetic resonance (¹H NMR), and the fracture surface of the composites was observed by scanning electron microscope (SEM) and atomic force microscopy. At room temperature and − 70°C, the maximum values of elongation at break were 15.78% and 12.55% with 10 wt% ESR. Compared with those of neat epoxy resin, the values of elongation at break of the composite were increased by 50.86% and 36.12%. The results of dynamic mechanical analysis also showed that the toughness of the modified resin had been improved. The SEM images of the fracture surfaces suggested that the fracture mode of the modified resin changed from brittle one to plastic one because of the addition of ESR-6, which further confirmed the toughening effect of ESR-6. These research results may provide a new strategy for enhancing the low-temperature toughness of epoxy resins.