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.     

Synthesis and modification of a naphthalene-containing trifunctional epoxy resin for electronic applications

A series of trifunctional epoxy resins were successfully synthesized by the condensation of 2,6-dimethylol-4-methylphenol with phenol , cresol, 2,6-dimethylphenol or 2-naphthol, respectively, followed by epoxidation with a halohydrin. The structures of the synthesized triphenols were characterized by elemental analysis (EA), mass spectrometry (MS), and nuclear magnetic resonance (NMR) spectrometry, including ¹H-NMR and ¹³C-NMR. The resulted epoxy resins were cured with 4–4′-diaminodiphenyl sulfone (DDS), and the cured products were investigated. The cured trifunctional 2,6-bis-(2-glycidyloxy-1-naphthyl-methyl)-4-methyl phenyl glycidyl ether had the highest glass transition temperature, highest thermal stability, the lowest coefficient of thermal expansion, and lowest moisture absorption of the epoxy resins studied. The internal stress of cured naphthalene-containing epoxy resin was reduced by modification with 12 wt % amino-terminated polydimethyl siloxane (ATPDMS), while the glass transition temperature was only slightly depressed. Phase separation of the silicone rubber-modified epoxy matrix was characterized by SEM. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1907–1921, 1998     

Synthesis of tetrafunctional epoxy resins and their modification with polydimethylsiloxane for electronic application

High-performance tetrafunctional epoxy resins were synthesized by reacting a suitable tetraphenols which were obtained by the condensation of appropriate dialdehyde with phenol followed by epoxidation with a halohydrin. The structure of the synthesized tetraphenols was confirmed by infrared (IR), mass spectra (MS), and nuclear magnetic resonance (NMR) spectroscopy. Dispersed silicone rubbers were used to reduce the stress of the synthesized tetrafunctional epoxy resin cured with phenolic novolac resin for electronic encapsulation application. The dynamic viscoelastic properties and morphologies of neat rubber-modified epoxy networks were investigated. The thermal mechanical properties and moisture absorption of encapsulants formulated from the synthesized tetrafunctional epoxy resins were also studied. The results indicate that a low-stress, high glass transition temperature (T_g), and low-moisture-absorbing epoxy resin system was obtained for semiconductor encapsulation application. © 1996 John Wiley & Sons, Inc.     

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.     

Dispersed acrylate rubber-modified epoxy resins for electronic encapsulation

A process was developed to incorporate stable dispersed acrylate rubber particles in an epoxy resin matrix which greatly reduces the stress of cured epoxy resins for electronic encapsulation application. The effect of the alkyl group of the acrylate monomer on the phase separation of resultant elastomers from epoxy resin was investigated. The dispersed acrylate rubbers effectively reduce the stress of cured epoxy resins by reducing the flexural modulus, while the glass transition temperature (T_g) was hardly depressed. Electronic devices encapsulated with the dispersed acrylate rubber-modified epoxy molding compounds have exhibited excellent resistance to the thermal shock cycling test and resulted in an extended device use life.     

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.     

Polydimethylsiloxane containing isocyanate group-modified epoxy resin: Curing,characterization, and properties

A synthesized polydimethylsiloxane containing an isocyanate group was used to improve the flexibility and to reduce the internal stress of epoxy resin cured with MDA (4,4′-methylene dianiline). The effect of polysiloxane content on the curing kinetics of a novolac-type epoxy modified with an isocyanate group was investigated. It was found that the modified epoxy resin showed significant improvement in impact strength. The polysiloxane containing isocyanate groups effectively depressed the internal stress of cured epoxy resins by reducing the flexural modulus and the coefficient of thermal expansion, while the glass transition temperature was increased. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2739–2747, 1999     

Syntheses of epoxy‐bridged polyorganosiloxanes and the effects of terminated alkoxysilanes on cured thermal properties

A series of epoxy‐bridged polyorganosiloxanes have been synthesized by reacting multifunctional aminoalkoxysilanes with diglycidyl ether of bisphenol A (DGEBA) epoxy resin. The reactions of trifunctional 3‐aminopropyltriethoxysilane (APTES), difunctional 3‐aminopropylmethyldiethoxysilane (APMDS), and monofunctional 3‐aminopropyldimethylethoxysilane (APDES) with DGEBA epoxy have been monitored and characterized by FTIR, ¹H NMR, and ²⁹Si NMR spectra in this study. The synthesized epoxy‐bridged polyorganosiloxanes precursors, with different terminated alkoxysilane groups, are thermally cured with or without the addition of curing catalysts. Organometallic dibutyltindilaurate, and alkaline tetrabutylammonium hydroxide have been used as curing catalysts to investigate the thermal curing behaviors and cured properties of epoxy‐bridged polyorganosiloxanes precursors. The maximum exothermal curing temperatures of epoxy‐bridged polyorganosiloxanes precursors are found to appear around the same region of 120°C in DSC analysis. The addition of catalysts to the epoxy/APTES precursor shows significant influence on the cured structure; however, the catalysts exhibit less influence on the cured structure of epoxy‐APMDS precursor and epoxy/APDES precursor. Curing catalysts also show significant enhancement in increasing the thermal decomposition temperature (T_d50s) of cured network of trifunctional epoxy‐bridged polyorganosiloxane (epoxy/APTES). High T_d50s of 518.8 and 613.6 in the cured hybrids of epoxy/APTES and epoxy/APMDS precursors are also observed, respectively. When trialkoxysilane‐terminated epoxy‐bridged polyorganosiloxanes precursor are cured, with or without the addition of catalyst, no obvious T_g transition can be found in the TMA analysis of cured network. The cured network of trialkoxysilane‐terminated epoxy‐bridged polyorganosiloxanes also exhibits the lowest coefficient of thermal expansion (CTE) among the three kinds of alkoxysilane‐terminated epoxy‐bridged polyorganosiloxanes investigated. The organic–inorganic hybrid, from epoxy‐bridged polyorganosiloxanes after the thermal curing process, shows better thermal stability than the cured resin network of pure epoxy‐diaminopropane. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3491–3499, 2006     

Bio-based shape memory epoxy resin synthesized from rosin acid

A bio-based shape memory epoxy resin (DGEAPA) was synthesized from rosin to achieve the sustainability of shape memory epoxy resin, and its chemical structure was determined by FTIR and ¹H NMR. For comparison, a petroleum-based epoxy, diglycidyl ester of terephthalic acid (DGT) having one benzene ring, was also synthesized. The properties, including thermal and mechanical properties, as well as shape memory properties of the epoxy resins cured with poly(propylene glycol)-bis (2-aminopropyl ether) (D230), were studied by differential scanning calorimeter, dynamic mechanical analysis, thermogravimetric analysis, tensile test, and U-type shape memory test. The effect of the stoichiometric ratio n_DGEAPA/n_DGT on the properties was studied as well. The thermal and mechanical properties, including thermal stability, glass transition temperature, tensile strength, and modulus of the cured epoxy systems, were found to be increased with DGEAPA incremental content, and the cured neat rosin-based epoxy system exhibited the highest properties. Both the cured rosin-based epoxy and the cured DGEAPA showed significant shape memory performance. Meanwhile, the rosin ring structure made the cured rosin-based epoxy systems display excellent shape recovery fixity, while small lower shape recovery and shape recovery rate relative to the cured neat DGT system. Therefore, the rosin-based epoxy resin has a great potential in the shape memory material applications.     

Synthesis,characterization, and properties of multifunctional naphthalene-containing epoxy resins cured with cyanate ester

Multifunctional naphthalene-containing epoxy resins derived from 2,7-dihydroxylnaphthalene were synthesized and the intermediates were characterized by Fourier transform infrared spectroscopy, elemental analysis, and mass spectrometry. The cured products from naphthalene-containing epoxy resin and the dicyanate ester of bisphenol A (DCBA) exhibited a better T_g and a lower coefficient of thermal expansion than those of the commercial epoxy system. The glass transition temperature, thermal stability, and moisture absorption were found to increase with the epoxy functionality when naphthalene-containing epoxy resins were cured with DCBA. Thermogravimetric analyses revealed that the DCBA-cured system had a better thermal stability than that of the 4,4′-diaminodiphenylsulfone (DDS)-cured system. The addition of a metallic catalyst into the epoxy resin/cyanate ester system not only facilitated the cyclotrimerization of the cyanate ester but also the polyetherification of the epoxy resin. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1611–1622, 1999     

Reaction kinetics,thermal properties of tetramethyl biphenyl epoxy resin cured with aromatic diamine

Epoxy resins, 4, 4′‐diglycidyl (3, 3′, 5, 5′‐tetramethylbiphenyl) epoxy resin (TMBP) containing rigid rod structure as a class of high performance polymers has been researched. The investigation of cure kinetics of TMBP and diglycidyl ether of bisphenol‐A epoxy resin (DGEBA) cured with p‐phenylenediamine (PDA) was performed by differential scanning calorimeter using an isoconversional method with dynamic conditions. The effect of the molar ratios of TMBP to PDA on the cure reaction kinetics was studied. The results showed that the curing of epoxy resins contains different stages. The activation energy was dependent of the degree of conversion. At the early of curing stages, the activation energy showed the activation energy took as maximum value. The effects of rigid rod groups and molar ratios of TMBP to PDA for the thermal properties were investigated by the DSC, DMA and TGA. The cured 2/1 TMBP/PDA system with rigid rod groups and high crosslink density had shown highest T_g and thermal degradation temperature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

The synthesis and properties of tetrafunctional epoxy resins

N,N,N′,N′-tetraglycidyl-4,4′-diaminodiphenylalkane epoxy resins with alkyl substituents on the methylene carbon were synthesized and characterized. The thermal and dynamic mechanical properties of these resins when cured with diaminodiphenylsulfone were compared with those of the cured unsubstituted epoxy resin. Although the resins have similar structures, the cured resin from the unsubstituted epoxy has the higher polymer decomposition temperature and glass transition temperature. The substituted epoxy resins have higher dynamic Young's moduli and loss moduli.     

Synthesis,thermal properties,and flame retardance of phosphorus‐containing epoxy‐silica hybrid resins

A novel epoxy resin modifier, phosphorus‐containing epoxide siloxane (DPS) with cyclic phosphorus groups in the Si O network, was prepared from the reaction of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) with polyhedral‐oligomeric siloxanes, which was synthesized by the sol–gel reaction of 3‐glycidoxypropyltrimethoxysilane. DPS was confirmed by Fourier transform infrared and ²⁹Si NMR measurement, and then was employed to modify epoxy resin at various ratios, with 4,4‐diaminodiphenyl‐methane as a curing agent. In order to make a comparison, DOPO‐containing epoxy resins were also cured under the same conditions. The resulting organic–inorganic hybrid epoxy resins modified with DPS exhibited a high glass transition temperature (T_g), a good thermal stability, and a high limited oxygen index. In addition, the tensile strength of cured products was also rather desirable. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

环氧树脂/三羟甲基三聚氰胺硅化物固化体系阻燃性能与耐热性研究

利用三聚氰胺和甲醛合成了三羟甲基三聚氰胺（TMM）,将其与正硅酸乙酯(TEOS)反应得到三羟甲基化三聚氰胺硅化物（TMMSi）。将TMMSi与环氧树脂复合,采用4,4'-二氨基二苯基甲烷(DDM)作固化剂来制备环氧树脂/TMMSi固化物,并对固化物的热性能和阻燃性能进行了分析。结果表明,与环氧树脂/TMM固化物相比,环氧树脂/TMMSi固化物的玻璃化转变温度变化较小,高温耐热性提高不明显,但是阻燃性能得到了大幅度提高。当TMMSi含量为15份时,环氧树脂/TMMSi固化物的极限氧指数达到29.6 %,比纯环氧树脂固化物提高了40 %。     

Synthesis,characterization, and properties of silicone–epoxy resins

Silicone–epoxy (SiE) resins were synthesized through the hydrolytic condensation of 2‐(3,4‐epoxycyclohexylethyl) methyldiethoxysilane (EMDS) and the cohydrolytic condensation of EMDS with dimethyldiethoxysilane. Structural characterization was carried out by ¹H‐NMR, ²⁹Si‐NMR, and mass spectrometry analysis; the resins were linear oligomers bearing different numbers of pendant epoxy groups, and the average number of repeat Si O units ranged from 6 to 11. Methyhexahydrophthalic anhydride was used to cure the SiE resins to give glassy materials with high optical clarity. The cured SiE resins showed better thermal stability and higher thermal and UV resistances than a commercial light‐emitting diode package material (an epoxy resin named CEL‐2021P). The effect of the epoxy value on the thermal and mechanical properties and the thermal and UV aging performances of the cured SiE resins were investigated. The SiE resins became more flexible with decreasing epoxy value, and the resin with the moderate epoxy value had the highest thermal and UV resistances. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of siliconized epoxy‐1,2‐bis(maleimido)ethane intercrosslinked matrix materials

Novel intercrosslinked networks of siliconized epoxy‐1,2‐bis(maleimido)ethane matrix systems are developed. The siliconization of epoxy resin is carried out by using 5–15% hydroxyl‐terminated poly(dimethylsiloxane) with γ‐aminopropyltriethoxysilane as a crosslinking agent and dibutyltin dilaurate as a catalyst. The siliconized epoxy systems are further modified with 5–15% 1,2‐bis(maleimido)ethane and cured by using diaminodiphenylmethane. The prepared neat resin castings are characterized for their mechanical properties. Mechanical studies indicate that the introduction of siloxane into these epoxy resins improves the toughness with a reduction in the stress–strain values, whereas incorporation of bismaleimide (BMI) into the epoxy resin improves the stress–strain properties with a lowering of the toughness. The introduction of both siloxane and BMI into the epoxy resin influences the mechanical properties according to their content percentages. Differential scanning calorimetry (DSC), thermogravimetry, and heat distortion temperature analyses are also carried out to assess the thermal behavior of the matrix materials that are developed. DSC thermograms of the BMI modified epoxy systems show unimodal reaction exotherms. The glass‐transition temperature, thermal degradation temperature, and heat distortion temperature of the cured BMI modified epoxy and siliconized epoxy systems increase with increasing BMI content. The water absorption behavior of the matrix materials is also studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3808–3817, 2003     

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     

MODIFICATION OF SILICONIZED EPOXY RESIN USING MULTIFUNCTIONAL SILANES

Silane coupling agents, namely 3-[(2–aminoethyl)amino]propyltrimethoxysilane (AETMS), 3-[(2–maleicmonoamido)maleicmonoamido]propyltrimethoxysilane (MMTMS) and 3-[(2–maleicdiamido)maleicdiamido]propyltrimethoxysilane (MDTMS), were synthesized and characterized using FT–IR and viscosity studies. The silane coupling agents developed in the present investigation were utilized for coupling hydroxyl terminated polydimethylsiloxane with epoxy matrix and cured with hexamethylenediamine and diaminodiphenylmethane. The siliconized epoxy system developed using MDTMS and cured with diaminodiphenylmethane yielded higher glass transition temperature, better thermal stability and imparts higher crosslinking density due to its higher functionality (pentafunctional) than AETMS and MMTMS (trifunctional). Diamine–cured siliconized epoxy resins coupled with AETMS, MMTMS and MDTMS can be used for the development of high–performance advanced composites.     

New antimicrobial epoxy‐resin‐bearing Schiff‐base metal complexes

New epoxy resins, ER₁–M(II) and ER₂–M(II) (molar ratio of epichlorohydrin), bearing Schiff‐base metal complexes were prepared by the condensation of epichlorohydrin with Schiff‐base metal complexes (L₂M, azomethine metal complexes) in 2 : 1 and 1.25 : 1 molar ratios, respectively, in an alkaline medium. The synthesized epoxy resins were characterized by various instrumental techniques, such as analytical, spectral, and thermal analysis. The epoxide equivalent weight (g/equiv) and epoxy value (equiv/100 g) of the synthesized epoxy resins were measured by standard procedures. The results of thermogravimetric analysis ascribed that ER₂–M(II) showed better heat‐resistance properties than ER₁–M(II) epoxy resin. The glass‐transition temperatures of all of the synthesized polymers were in the range 153–230°C. The antimicrobial activities of these resins were screened against some bacteria and against some yeast with an agar well diffusion method. All of the synthesized resins showed promising antimicrobial activities. Cu(II)‐chelated resin showed wider effective antibacterial and antifungal activities than the other resins because of a higher stability constant. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and Application of a New Curing Agent for Epoxy Resin

A new curing agent based on palmitoleic acid methyl ester modified amine (PAMEA) for epoxy resin was synthesized and characterized. Diglycidyl ether of bisphenol A (DGEBA) epoxy resins cured with different content of PAMEA along with diethylenetriamine (DETA) were prepared. The mechanical properties, dynamic mechanical properties, thermal properties, and morphology were investigated. The results indicated that the PAMEA curing agent can improve the impact strength of the cured epoxy resins considerably in comparison with the DETA curing agent, while the modulus and strength of the cured resin can also be improved slightly. When the PAMEA/epoxy resin weight ratio is 30/100, the comprehensive mechanical properties of the cured epoxy resin are optimal; at the same time, the crosslinking density and glass transition temperature of the cured epoxy resin are maximal.