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.     

New epoxy resins based on recycled poly(ethylene terephthalate) as organic coatings

Glycolysis of poly(ethylene terephthalate), PET, waste using trimethylol propane (TMP), triethanolamine (TEA), diethylene glycol (DEG) and diethanolamine (DEA) was used to produce suitable hydroxy-oligomers for epoxy. The glycolyzed products were reacted with epichlorohydrine to prepare a series of di- and tetraglycidyl epoxy resins with different molecular weights. The glycolysis was carried out in presence of manganese acetate as a catalyst at normal and high pressure in presence and absence of xylene at 210 °C. The produced resins were cured with different mole ratios of 1-(2-amino ethyl) piprazine as curing agent at room temperature. 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 based on glycolyzed oligomer of PET and DEA have excellent chemical resistances as organic coatings among other cured resins.     

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.     

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 naphthalene containing aralkyl novolac epoxy resins for electronic application

Naphthalene containing aralkyl novolac epoxy resins were synthesized by the condensation of p‐xylylene glycol with 2,7‐dihydroxynaphthalene or 2‐naphthol followed by the epoxidation of the resulting aralkyl novolacs with epichlorohydrin. The mechanical and dynamic viscoelastic properties of cured aralkyl novolac epoxy resins were investigated. Comparisons of mono‐ and di‐functional naphthalene containing aralkyl novolac epoxy resins based on thermal and moisture absorption properties were also studied. The results indicate that a naphthalene containing aralkyl epoxy resin made from the difunctional naphthol has a low coefficient of thermal expansion, high heat resistance, and low moisture absorption.     

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     

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     

Mesua ferrea L. seed oil‐based epoxy resins

Exhaustion of fossil fuels, tremendous increase of materials demand, and unpredictable prices of petroleum based products urge upon the sustainable development. Three different epoxy resins have been synthesized from monoglyceride of Mesua ferrea L. seed oil and epichlorohydrin with and without other dihydroxy compound like tetrabromobisphenol‐A (TBPA) and bisphenol‐A (BPA). The synthesized epoxy resin were characterized by measurement of physical properties like epoxy equivalent, viscosity, hydroxyl value, saponification value, acid value, etc., and spectroscopic techniques like FTIR and ¹H NMR. High thermostability with initial decompositions temperature of 225–265°C was observed for the cured resins and 75 mol % BPA based resin exhibits the highest thermostability. Newtonian flow behavior was observed for all resins as indicated by the rheometric study (CVO 100). The flame retardency rating of TBPA based epoxy was found to be V1 as tested by UL 94. The performance characteristics as coating materials were studied by the measurement of gloss, impact resistance, scratch hardness, tensile strength, elongation at break, adhesive strength, and chemical resistance. The results indicate the suitability of the synthesized resins as coating materials. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of a novel curing agent containing organophosphorus and its application in flame‐retarded epoxy resins

A novel amine‐terminated and organophosphorus‐containing compound m‐aminophenylene phenyl phosphine oxide oligomer (APPPOO) was synthesized and used as curing and flame‐retarding agent for epoxy resins. Its chemical structure was characterized by Fourier transform infrared (FTIR) spectroscopy, ¹H nuclear magnetic resonance (¹H NMR), ¹³C nuclear magnetic resonance, and ³¹P nuclear magnetic resonance. The flame‐retardant properties, combusting performances, and thermal degradation behaviors of the cured epoxy resins were investigated by limiting oxygen index (LOI), vertical burning test (UL‐94), cone calorimeter test, and thermogravimetric analysis. The EPO/APPPOO thermosets passed V‐1 rating with the thickness of 3.0 mm and the LOI value reached 34.8%. The thermosets could pass V‐2 rating when the thickness of the samples was 1.6 mm. The cone calorimeter test demonstrated that the parameters of EPO/APPPOO thermosets including heat release rate and total heat release significantly decreased compared with EPO/PDA thermosets. Scanning electron microscopy revealed that the incorporation of APPPOO into epoxy resins obviously accelerated the formation of the compact and stronger char layer to improve flame‐retardant properties of the cured epoxy resins during combustion. The mechanical properties and water resistance of the cured epoxy resins were also measured. After the water‐resistance test, EPO/APPPOO thermosets still remained excellent flame retardant and the water uptake was only 0.4%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41159.     

Synthesis and Characterization of Tetra-Functional Epoxy Resins from Rosin

Tetra functional epoxy resins were prepared by the reaction of diethanolamine with Diels–Alder adducts of rosin ketone. These adducts were reacted with epichlorohydrine in the presence of NaOH as a catalyst to produce epoxy resins. The resins obtained were characterized by IR and ¹H NMR spectroscopy. The curing behaviours of these resins with their poly (amide-imide) derivatives were investigated by viscosity measurements. The curing activation energy was calculated from the gel time and critical viscosity measurements. The curing exotherms of the epoxy resins produced with poly (amide-imide) hardeners were investigated. The curing and gel times of the resins produced show slight differences between the synthesized resins. The chemical resistances and mechanical properties of the cured films were evaluated. The produced coats show high stability for salt spray at a duration time of 563 h.     

Structure and viscoelastic properties of epoxy resins prepared from four-nuclei novolacs

The relation between the structure and the viscoelastic properties of seven kinds of epoxy resins was studied. Seven tetraglycidylethers were synthesized from four-nuclei novolacs in which the positions of methylene linkage or number of kind of substituents were different. These epoxy compounds were cured with diaminodiphenylmethane as a hardener. From the viscoelastic properties of the fully cured resins with the hardener, characteristic properties such as glass transition temperature (T_g), average molecular weight between crosslinking points (M̄_c), and front factor (ϕ) were obtained. It was concluded that higher linearity in the main chain of epoxy resins gave a cured resin with a higher T_g, a smaller M̄_c, and a larger ϕ.     

Synthesis of epoxy curing agents containing different ring structures and properties investigation of the cured resins

Two kinds of aliphatic epoxy curing agents containing ring structures were synthesized from rosin acid and isosorbide, respectively. They were cured with diglycidyl ether bisphenol A (DER331) and the ultimate propertied of the cured resins were investigated. For comparison, the petroleum‐based curing agent containing planar benzene ring was synthesized from terephthalic acid. The chemical structures of the synthesized curing agents were identified by Fourier transform‐infrared and H‐nuclear magnetic resonance. The ultimate properties of the cured epoxy resins were investigated by thermogravimetric analysis and dynamic mechanical analysis. Especially, the effects of ring structure on their shape memory properties were studied in terms of shape fixity, shape recovery, and shape recovery time. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44219.     

Synthesis of rosin‐based flexible anhydride‐type curing agents and properties of the cured epoxy

BACKGROUND: Although rosin acid derivatives have received attention in polymer synthesis in recent years, to the best of our knowledge, they have rarely been employed as epoxy curing agents. The objective of the study reported here was to synthesize rosin‐based flexible anhydride‐type curing agents and demonstrate that the flexibility of a cured epoxy resin can be manipulated by selection of rosin‐based anhydride‐type curing agents with appropriate molecular rigidity/flexibility. RESULTS: Maleopimarate‐terminated low molecular weight polycaprolactones (PCLs) were synthesized and studied as anhydride‐type curing agents for epoxy curing. The chemical structures of the products were confirmed using ¹H NMR spectroscopy and Fourier transform infrared spectroscopy. Mechanical and thermal properties of the cured epoxy resins were studied. The results indicate that both the epoxy/anhydride equivalent ratio and the molecular weight of PCL diol play important roles in the properties of cured resins. CONCLUSION: Rosin‐based anhydride‐terminated polyesters could be used as bio‐based epoxy curing agents. A broad spectrum of mechanical and thermal properties of the cured epoxy resins can be obtained by varying the molecular length of the polyester segment and the epoxy/curing agent ratio. Copyright © 2009 Society of Chemical Industry     

Phosphorous‐containing epoxy resins from a novel synthesis route

The ? P(O)‐H in 9,10‐dihydro‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) was used as an active group to react with the carbonyl group in 4,4′‐dihydroxybenzophenone (DHBP) to result a novel phosphorous‐containing biphenol compound (DOPO‐2OH). Phosphorous‐containing epoxy resins were therefore obtained from reacting DOPO‐2OH with epichlorohydrin or with diglycidylether bisphenol A. The synthesized compounds were characterized with FTIR, ¹H and ³¹P NMR, elemental analysis, and epoxide equivalent weight titration to demonstrate the their chemical structures. Cured epoxy resins were prepared via thermal curing the epoxy resins with various curing agents. Thermal analysis results (differential scanning calorimetry and thermogravimetric analysis) revealed that these cured epoxy resins exhibited high glass transition temperatures and high thermal stability. High char yields at 700°C and high LOI (limited oxygen index) values were also found for the cured epoxy resins to imply that the resins were possessing high flame retardancy. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1697–1701, 2002     

A novel UV‐curable epoxy acrylate resin containing arylene ether sulfone linkages: Preparation,characterization, and properties

UV‐curing processes are used in industrial applications because of their advantages such as high‐speed applications and solvent‐free formulations at ambient temperature. UV‐curable epoxy acrylate resins containing arylene ether sulfone linkages (EAAES) were synthesized through the condensation of bis(4‐chlorophenyl)sulphone and bisphenol‐A, followed by end‐caping of epichlorohydrin and subsequently acrylic acid. UV‐cured coatings were formulated with epoxy acrylates, reactive diluents such as pentaerythritol tri‐acrylate and pentaerythritol dia‐crylate and photoinitiator. Fourier transfer infrared, ¹H NMR, and thermal gravimetrical analysis were employed to investigate the structures and thermal properties of the EAs films. The introduction of EAAES into epoxy acrylate substantially improves its thermal properties and thermo‐oxidative stability at high temperatures. In addition, the acrylate containing arylene ether sulfone linkages can also improve pencil hardness and chemical and solvent resistance of the epoxy acrylate. The obtained UV‐curable epoxy acrylate containing arylene ether sulfone linkages is promising as oligomer for UV‐curable coatings, inks, and adhesives in some high‐tech regions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41067.     

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     

Synthesis of bio-based epoxy resin from gallic acid with various epoxy equivalent weights and its effects on coating properties

The bio-based epoxy resins for coating application were synthesized from gallic acid (GA) in various molar ratios with epichlorohydrin (ECH). The reaction was carried out in the presence of sodium hydroxide (NaOH) and phase-transfer catalyst tetrabutylammonium bromide. The reaction progress rate at various molar ratios as 1:8, 1:12, and 1:16 with respect to time was monitored by calculating the epoxy content. The epoxy content value increases in the product as the molar ratio of GA to ECH increases. Epoxy equivalent weight of products was evaluated by physiochemical method and structure illustrated by Fourier transform infrared and ¹H-nuclear magnetic resonance spectroscopy. This bio-based epoxy resin was cured with polyamide hardener, and the coating properties such as mechanical, chemical, and solvent resistance were studied. The cured films have been evaluated for glass transition temperature (T _g) and thermal behavior by a differential scanning calorimeter and thermogravimetric analysis, respectively. The bio-based epoxy coatings show interesting mechanical, chemical, and thermal properties as compared to the conventional epoxy resin. The gel and water absorption of polyamide-cured coatings has also been evaluated.     

Synthesis,characterization, and degradation investigation of water‐soluble β‐cyclodextrin‐based epoxy resins

A series of β‐cyclodextrin‐based epoxy resins were synthesized with different epoxy equivalent weights. Their chemical structures were characterized with Fourier Transform Infrared Spectroscopy (FTIR) and Nuclear Magnetic Resonance Spectroscopy (NMR) examination. These epoxy resins were cured using L ‐arginine as a curing agent, and the degradation behavior of the cured resins was evaluated under different acidic buffer solutions at 37°C. The degradable behavior of such epoxy resins suggested potential applications as environment friendly materials. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of a novel cross‐linked organophosphorus‐nitrogen containing polymer and its application in flame retardant epoxy resins

A novel cross‐linked organophosphorus–nitrogen polymetric flame retardant additive poly(urea tetramethylene phosphonium sulfate) defined as PUTMPS was synthesized by the condensation polymerization between urea and tetrahydroxymethyl phosphonium sulfate. Its chemical structure was well characterized by Fourier transform infrared (FTIR) spectroscopy, ¹³C and ³¹P solid‐state nuclear magnetic resonance. The synthesized PUTMPS and curing agent m‐phenylenediamine were blended into epoxy resins to prepare flame retardant epoxy resin thermosets. The effects of PUTMPS on fire retardancy and thermal degradation behavior of EP/PUTMPS thermosets were investigated by limiting oxygen index (LOI), vertical burning test (UL‐94), cone calorimeter measurement, and thermalgravimetric analysis (TGA) tests. The surface morphologies and chemical compositions of char residues for cured epoxy resins were investigated by scanning electron microscopy and X‐ray photoelectron spectroscopy (XPS), respectively. Water resistant properties of epoxy resin thermosets were evaluated by putting the samples into distilled water at 70°C for 168 h. The results demonstrated that the EP/12 wt% PUTMPS thermosets successfully passed UL‐94 V‐0 flammability rating and the LOI value reached 31.3%. The TGA results indicated that the incorporation of PUTMPS promoted epoxy resin matrix decomposed and char forming ahead of time, which led to a higher char yield and thermal stability for epoxy resin thermosets at high temperature. The morphological structures and analysis of XPS for the char residues of the epoxy resin thermosets shown that PUTMPS benefited to the formation of a sufficient, more compact, and homogeneous char layer with rich flame retardant elements on the materials surface during burning, which prevented the heat transmission and diffusion, limited the production of combustible gases, inhibited the emission of smoke, and then led to the reduction of the heat release rate and smoke produce rate. After water resistance tests, EP/12 wt% PUTMPS thermosets still remained excellent flame retardancy. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of the NCO/OH ratio on the properties of Mesua Ferrea L. seed oil‐modified polyurethane resins

A series of polyurethane resins with varying NCO/OH ratios (0.8–2.0) has been synthesized from the monoglyceride of Mesua Ferrea L. seed oil, poly(ethylene glycol) (M_n, 200 g mol^?1) and 2,4‐toluene diisocyanate in the presence of dibutyl tin dilaurate as the catalyst. The effects of the NCO/OH ratios of the synthesized resins on the physical properties, such as hydroxy values, acid values, saponification values, iodine values, specific gravities and isocyanate values have been studied. The formation of the polyurethane resins was confirmed by viscosity measurements, and FTIR, UV and ¹H NMR spectroscopic studies. Performance characteristics, such as impact resistance, flexibility, gloss, hardness, adhesive strength and chemical resistance, of the cured resins were investigated as a function of the varying NCO/OH ratios, with an influence of these ratios being observed for most of the above properties. Thermogravimetric analysis (TGA) demonstrated that the thermal stabilities of the cured resins increased with an increase in the NCO/OH ratios. The amounts of char residues at 550 °C were also found to be greater for higher NCO/OH ratios of the oil‐modified polyurethane resins. Copyright © 2005 Society of Chemical Industry