Hybrid Polymer Networks of Epoxy Resin and Substituted Phenolic Novolacs

Hybrid polymer networks of diglycidyl ether of bisphenol (DGEBA) resin and phenolic novolac resins were prepared and tested for mechanical properties, hardness, and water absorption. The novolacs employed were based on each of phenol and substituted phenols such as p-cresol, t-butyl phenol, and cardanol. Cardanol is the main constituent of cashew nut shell liquid (CNSL), a renewable resource. Blends containing 10–15 wt% of novolac resin show substantial improvement in properties. These properties show a declining trend with higher novolac loading. The stoichiometric ratio between phenol and formaldehyde in the novolacs was optimized (1:0.8) for maximum property enhancement. The property profiles of the epoxy/novolac networks show that novolacs are effective modifiers for commercial epoxy resin. Incorporation of novolacs of substituted phenols results in relatively greater improvement in energy absorption during failure.     

Synthesis of novolac on the basis of bisphenol A as curing agent for epoxy resins

Bisphenol A novolacs were synthesized in a melting process using paraformaldehyde, and in a solution process using a formalin solution and oxalic acid catalyst. ¹H-NMR investigations show a higher content of methylene bridges in the novolacs synthesized in a melting process. These novolacs were analysed by HPLC, GPC, DSC and FT-IR spectroscopy. The molecular masses were determined by vapour pressure osmometry. The results were shown to be related with the molar ratio of the components. The bisphenol A novolacs were used as curing agents for epoxy resins. There exists a dependence of the gel times on the content of methylene bridges; this dependence is influenced by temperature. The activation energy for gel formation is nearly the same in all curing reactions investigated. The networks synthesized were investigated by thermomechanical analysis.     

Effect of a curing accelerator on the glass transition temperature of non-stoichiometric epoxy amine networks

Networks were prepared from Bisphenol A diglycidylether and 4,4′-diaminodiphenylmethane both in the presence of different amounts of imidazole and in the absence of any accelerator. The ratio of epoxy groups to amino hydrogen was varied: the networks were made with amino hydrogen excess, a stoichiometric ratio of epoxy groups to amino hydrogen, and an epoxy excess. The resulting networks were investigated by thermomechanical analysis, by torsion pendulum analysis and by uniaxial compression modulus measurements in the rubbery-plateau zone. Further characterization was done by sol gel analysis of the cured samples. It was shown that imidazole does not significantly influence the glass transition temperature and the soluble content of the samples of an excess of amino hydrogen was used. In the case of a stoichiometric ratio of epoxy groups to amino hydrogen and in the case of an epoxy excess, imidazole considerably influences the glass transition temperature of the networks. A dependence of the soluble content of the samples on imidazole concentration used for network synthesis was found mainly in epoxy excess systems.     

New bisphenol novolac epoxy resins for marine primer steel coating applications

Bisphenol derived from reaction of phenol with benzaldehyde was prepared in the presence of sulfuric acid as catalyst. Bisphenol novolacs were synthesized in both melting and solution processes using p-formaldehyde and formalin solution in the presence of oxalic acid catalyst. ¹H NMR analysis shows a high methylene bridge contents using the novolacs synthesized in a melting process. The bisphenol novolac epoxy resin was prepared by reaction with epichlorohydrine in the presence of sodium hydroxide as a catalyst. The prepared novolac epoxy resins were cured with 1,2-amino ethyl piperazine (AEP) as a curing agent. The cured resins were evaluated as organic coating for steel. The mechanical properties of the cured epoxy resins were evaluated by measuring both impact resistance and hardness. The chemical resistances of the cured resins were evaluated through salt spray resistance, hot water immersion, solvent resistance, acid and alkali resistance measurements. The data indicate that the cured epoxy resins have excellent chemical resistances as organic coatings among other cured resins.     

Phenolic‐epoxy matrix curable by click chemistry—synthesis,curing, and syntactic foam composite properties

Alkyne functional phenolic resin was cured by azide functional epoxy resins making use of alkyne‐azide click reaction. For this, propargylated novolac (PN) was reacted with bisphenol A bisazide (BABA) and azido hydroxy propyloxy novolac (AHPN) leading to triazole‐linked phenolic‐epoxy networks. The click cure reaction was initiated at 40–65°C in presence of Cu₂I₂. Glass transition temperature (Tg) of the cured networks varied from 70°C to 75°C in the case of BABA‐PN and 75°C to 80°C in the case of AHPN‐PN. DSC and rheological studies revealed a single stage curing pattern for both the systems. The cured BABA‐PN and AHPN‐PN blends showed mass loss above 300°C because of decomposition of the triazole rings and the novolac backbone. Silica fiber‐reinforced syntactic foam composites derived from these resins possessed comparable mechanical properties and superior impact resistance vis‐a‐vis their phenolic resin analogues. The mechanical properties could be tuned by regulating the reactant stoichiometry. These low temperature addition curable resins are suited for light weight polymer composite for related applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41254.     

Kinetics and thermal characterization of epoxy‐amine systems

The curing behavior of epoxy resins was analyzed based on a simple kinetic model. We simulated the curing kinetics and found that it fits the experimental data well for both diglycidylether of bisphenol A–4,4′‐methylene dianiline and diglycidylether of bisphenol A–carboxyl‐terminated butadiene acrylonitrile–4,4′‐methylene dianiline systems. The kinetic results showed the curing of epoxy resins involves different reactive process and reaction stages, and the value of activation energy is dependent on the degree of conversion. By analyzing the effect of vitrification, at low curing temperature, we found the curing reaction at the later stage was practically diffusion‐controlled for unmodified resin, and the rubber component did not markedly decrease T_g at the early stage of reaction as would be expected. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2401–2408, 1999     

Synthesis of bisphenol a novolac epoxy resins for coating applications

Bisphenol A novolacs were synthesized in both melting and solution processes using p‐formaldehyde and formalin solution in presence of oxalic acid catalyst, respectively. Hydrogen nuclear magnetic resonance, ¹H NMR, investigations show a high methylene bridge contents in the novolacs synthesized in a melting process. These novolacs were analyzed by gel permation chromatography (GPC) and fourier transform infrared spectroscopy (FTIR). The bisphenol A novolac was cured with 1‐(2‐amino ethyl) piprazine (AEP) as a curing agent for epoxy resins. The cured resins were evaluated as organic coating for steel. The mechanical properties of the cured epoxy resins were evaluated. The chemical resistances of the cured resins were evaluated through salt spray resistance, hot water, solvents, acid and alkali resistance measurements. The data indicate that the cured epoxy resins have excellent chemical resistances as organic coatings among other cured resins. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Macro- and microgelation in the homopolymerization of diepoxides initiated by tertiary amines

Summary The homopolymerization of an epoxy resin based on diglycidylether of bisphenol A (DGEBA), initiated by benzyldimethylamine (BDMA), was analyzed in the 80°C–140°C temperature range. An heterogeneous network characterized by regions of different glass transition temperature, was obtained. Microgels appeared early in the polymerization while an increase in the reactivity of the second epoxy group of a DGEBA molecule after reaction of the first one, was inferred from size exclusion chromatograms (SEC), obtained at different overall conversions. Both experimental findings were qualitatively explained through an intramolecular chain transfer step that regenerates the initiator in the proximity of pendant epoxy groups. The increase in the polymerization temperature produced an increase in the macroscopic gel conversion and a decrease in the glass transition temperature of regions of high crosslink density. This was ascribed to the increase in the ratio of intramolecular chain transfer over propagation rates, leading to shorter primary chains.     

Low dielectric thermoset. I. Synthesis and properties of novel 2,6‐dimethyl phenol‐dicyclopentadiene epoxy

A 2,6‐dimethyl phenol‐dicyclopentadiene novolac was synthesized from dicyclopentadiene and 2,6‐dimethyl phenol, and the resultant 2,6‐dimethyl phenol‐dicyclopentadiene novolac was epoxidized to 2,6‐dimethyl phenol‐dicyclopentadiene epoxy. The structures of novolac and epoxy were confirmed by Fourier transform infrared spectroscopy (FTIR), elemental analysis, mass spectroscopy (MS), nuclear magnetic resonance spectroscopy (NMR), and epoxy equivalent weight titration. The synthesized 2,6‐dimethyl phenol‐dicyclopentadiene epoxy was then cured with 4,4‐diaminodiphenyl methane (DDM), phenol novolac (PN), 4,4‐diaminodiphenyl sulfone (DDS), and 4,4‐diaminodiphenyl ether (DDE). Thermal properties of cured epoxy resins were studied by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), dielectric analysis (DEA), and thermal gravimetric analysis (TGA). These data were compared with those of the commercial bisphenol A epoxy system. Compared with the bisphenol A epoxy system, the cured 2,6‐dimethyl phenol‐ dicyclopentadiene epoxy resins exhibited lower dielectric constants (～3.0 at 1 MHz and 2.8 at 1 GHz), dissipation factors (～0.007 at 1 MHz and 0.004 at 1 GHz), glass transition temperatures (140–188°C), thermal stability (5% degradation temperature at 382–404°C), thermal expansion coefficients [50–60 ppm/°C before glass‐transition temperature (T_g)], and moisture absorption (0.9–1.1%), but higher modulus (～2 Gpa at 60°C). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2607–2613, 2003     

Synthesis, characterization, and properties of novel novolac epoxy resin containing naphthalene moiety

A series of novel novolac epoxy resins containing naphthalene moiety with different molecular weights were synthesized via condensation of bisphenol A and 1-naphthaldehyde, followed by epoxidation with epichlorohydrin. The chemical structure of the naphthalene epoxy thus obtained was characterized using FTIR, ¹H NMR spectra and GPC analyses. The naphthalene epoxy was cured with 4,4′-diaminodiphenyl sulfone (DDS) and the cured products were characterized with thermogravimetric analysis, dynamic mechanical analysis, and X-ray diffraction. Compared with the diglycidyl ether of bisphenol A (DGEBA), the cured naphthalene epoxy resin showed remarkably higher glass transition temperatures (T_gs), enhanced thermal stability and better moisture resistance. When the molar ratio of 1-naphthaldehyde to bisphenol A was 0.67, the optimal thermal resistance was observed.     

Synthesis of aralkyl novolac epoxy resins and their modification with polysiloxane thermoplastic polyurethane for semiconductor encapsulation

A series of phenol‐based and naphthol‐based aralkyl epoxy resins were synthesized by the condensation of p‐xylylene glycol with phenol, o‐cresol, p‐cresol, or 2‐naphthol, respectively, followed by the epoxidation of the resulting aralkyl novolacs with epichlorohydrin. The incorporation of stable dispersed polysiloxane thermoplastic polyurethane particles in the synthesized epoxy resin's matrix was achieved via epoxy ring‐opening with the isocyanate groups of urethane prepolymer to form an oxazolidone. The mechanical and dynamic viscoelastic properties of cured aralkyl novolac epoxy resins were investigated. A sea‐island structure was observed in all cured rubber‐modified epoxy networks via SEM. The results indicate that a naphthalene containing aralkyl epoxy resin has a low coefficient of thermal expansion, heat resistance, and low moisture absorption, whereas phenol aralkyl type epoxy resins are capable of imparting low elastic modulus result in a low stress matrix for encapsulation applications. Modification of the synthesized aralkyl epoxy resins with polysiloxane thermoplastic polyurethane have effectively reduced the stress of cured epoxy resins, whereas the glass transition temperature was increased because of the formation of the rigid oxazolidone structure. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1905–1916, 1999     

Aminosiloxane-modified epoxy resins as microelectronic encapsulants

Amine-terminated poly(dimethylsiloxanes) (ATPDMS) were used to improve the toughness of a cresol-formaldehyde novolac epoxy resin cured with a phenolic novolac resin for electronic encapsulation application. The effect of molecular weight of amine-terminated polysiloxanes on the phase separation of the resultant elastomers from epoxy matrix were investigated. Mechanical and dynamic viscoelastic properties of siloxane-modified epoxy networks were also studied. The dispersed silicone rubbers effectively improve the toughness of cured epoxy resins by reducing the coefficient of thermal expansion and flexural modulus, while the glass transition temperature 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.     

Structure and viscoelastic properties of epoxy resins prepared from o-cresol novolacs

The relation between the structure and viscoelastic properties of the epoxy resins prepared from o-cresol novolacs was studied. Our model epoxy resins were two kinds of epoxy compounds synthesized from three-nuclei and four-nuclei o-cresol novolacs. In addition to these models, a commercially available o-cresol novolac-type epoxy resin was also studied. Each of the three epoxy compounds was cured with one of three kinds of novolacs, which were starting materials of the above-mentioned epoxy resins. Characteristic properties of the cured resins, such as glass transition temperature (T_g), average molecular weight between crosslinking points (M¯_c), and front factor (?) were obtained. It was concluded that the number of functional groups contained in the curing system almost dominated the viscoelastic properties of the cured resins.     

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.     

Photo-oxidation and photoprotection of the surface resin of a glass fiber–epoxy composite

The rapid photo-oxidation of the surface epoxy resin of a commercial seven-ply laminate (Scotchply 1009-26) is due principally to the epoxy novolac resin component. The photo-oxidation rate of this resin is eight times that of the other component, a bisphenol A epoxy resin. This rate depends on the conditions of cure, and photo-initiation occurs in part through aromatic carbonyl groups formed by oxidation of the methylene linkages of the novolac at the cure temperature (160–180°C). Inhibition of this thermal oxidation by vacuum cure or a chain-terminating antioxidant increases the photostability. Photoprotection of thin resin sections by the UV stabilizer 2-hydroxy-4-isooctoxybenzophenone and an epoxidized analog is assessed.     

Epoxy-based composite adhesives with improved lap shear strengths at high temperatures for steel-steel bonded joints

High-performance room temperature-cure epoxy structural adhesives utilizing simplified formulation are developed. The developed structural adhesive consists of diglycidyl ether of bisphenol A (DGEBA) and novolac epoxy blend as a base resin, micrometer-sized silica particles as a reinforcing filler, and triethylenetetramine as a curing agent. The developed ambient temperature-cure epoxy structural adhesive with optimized formulation exhibits outstanding properties including high glass transition temperature of 95°C, high thermal stability with degradation temperature at 5% weight loss of 364°C, exceptionally high rubbery plateau modulus of 320 MPa, good flame-retardant characteristics with limiting oxygen index of 40, and high single lap shear strength for single lap steel-steel bonded joint of 548 MPa at the temperature of 80°C. The silica-filled DGEBA/novolac epoxy composite adhesive is a potential candidate for applying as a structural adhesive for construction with long-term durability.     

Modification of epoxy resins with polysiloxane TPU for electronic encapsulation. II

Polyol or polysiloxane thermoplastic polyurethanes (TPU) were used to reduce micro-cracking in cresol–formaldehyde novolac epoxy resin cured with phenolic Novolac resin for electronic encapsulation application. A stable dispersion of TPU particles in an epoxy resin matrix was achieved via the epoxy ring opening with isocyanate groups of urethane prepolymer to form an oxazolidone. The effects of structure and molecular weight of TPU in reducing the stress of electronic encapsultant were investigated. The mechanical and dynamic viscoelastic properties and morphologies of TPU modified epoxy networks were also studied. A “sea-island” structure was observed via SEM. The dispersed polysiloxane TPU rubbers not only effectively reduce the stress of cured epoxy resins, by reducing flexural modulus and the coefficient of thermal expansion, but also increase the glass transition temperature because of the rigid oxazolidone structure formation. Electronic devices encapsulated with the polysiloxane TPU modified epoxy molding compounds exhibited excellent resistance to the thermal shock cycling test and resulted in extended device life. © 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.     

Effect of Phenol/Formaldehyde Stoichiometry on the Modification of Epoxy Resin Using Epoxidized Novolacs

ABSTRACT

Unmodified epoxy resins based on bisphenol A exhibit brittleness and low elongation after cure. This article reports the results of a study for improving the properties of epoxy resin by blending with suitable thermosets. Hybrid polymer networks of diglycidyl ether of bisphenol A (DGEBA) resin with epoxidized phenolic novolac resins (EPN) containing phenol and formaldehyde in different stoichiometric ratios were prepared by physical blending. The modified epoxy resins were found to exhibit improved mechanical and thermal properties compared to the neat resin. DGEBA resins containing 2.5 to 20 wt% of epoxidized novolac resins (EPN) prepared in various stoichiometric ratios (1:0.6, 1:0.7, 1:08, and 1:0.9) between phenol and formaldehyde were cured using a room temperature amine hardener. The cured samples were tested for mechanical properties such as tensile strength, modulus, elongation, and energy absorption at break. All the EPNs are seen to improve tensile strength, elongation, and energy absorption at break of the resin. The blend of DGEBA with 10 wt% of EPN-3 (1:0.8) exhibits maximum improvement in strength, elongation, and energy absorption. EPN loading above 10 wt% is found to lower these properties in a manner similar to the behavior of any filler material. The property profiles of epoxy–EPN blends imply a toughening action by epoxidized novolac resins and the extent of modification is found to depend on the molar ratio between phenol and formaldehyde in the novolac.     

双酚A型双邻苯二甲腈/酚醛树脂共混体系研究

双酚A型双邻苯二甲腈(BAPh)与酚醛树脂(novolac)通过熔融共混形成了预聚物(BAPh/novolac),经后续热处理制备了BAPh/novolac固化物。通过DSC,FTIR,TGA及流变性能测试研究了该共混体系的固化反应特性,固化物的热稳定性和热氧化稳定性。结果表明:该共混体系可以在无外加固化剂的条件下进行固化反应,固化物的玻璃化转变温度(Tg)达241℃。其固化物在空气和N2气氛中的起始分解温度为380～449℃,且在氮气下800℃残炭率达71%,表现出良好的热稳定性和热氧稳定性。