Structure and properties of a low viscosity acrylate based flexible epoxy resin

A series of low viscosity acrylate‐based epoxy resin (AE)/glycol diglycidyl ether (GDE) systems were prepared. The effect of GDE and low molecular weight polyamide (LPA) content on the rheological behavior, phase structure, damping, and mechanical properties were studied by differential scanning calorimeter (DSC), viscometer, scanning electron microscopy (SEM), dynamic mechanical thermal analysis (DMTA), and electro mechanical machine. The viscosity of the uncured AE systems decreased significantly after the incorporation of GDE. The damping properties were found to decrease slightly with the increasing GDE and LPA content. The tensile strength of the cured AE/GDE samples enhanced significantly after the incorporation of GDE with at least 150% improvement for all the samples while it decreased slightly with increasing LPA content. The AE/GDE cured systems were intended for future use as structural damping materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42959.     

Influence of epichlorohydrin content on structure and properties of high‐ortho phenolic epoxy fibers

The high‐ortho phenolic epoxy fibers (HPEFs) were prepared by the crosslinking of heat‐meltable spun filaments derived from melt‐spinning of the novolac epoxy resins copolymerized among phenol, formaldehyde, and epichlorohydrin (ECH) in the presence of zinc acetate and sulfuric acid catalyst, and cured in a combined solution of formaldehyde and hydrochloric acid. The resulting fibers were heat‐treated in N₂ at elevated temperature. Infrared (IR) spectrometer, thermogravimetric analysis (TGA), scanning electron microscope (SEM), and electrical tensile strength apparatus were employed to characterize the change of functional groups, thermal performance, microstructure of fibers, and mechanical properties. The results show that the addition of ECH in the precursor resin can increase the content of long alkyl ether linkage, and gain the peak of thermal stability and mechanical strength. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43375.     

Interaction and properties of epoxy‐amine system modified with poly(phthalazinone ether nitrile ketone)

An epoxy based on the tetraglycidyl 4,4′‐diaminodiphenyl‐ methane (TGDDM)/bisphenol A type novolac(F‐51) cured with 4,4′‐diaminidiphenysulfone (DDS) has been modified with Poly (phthalazinone ether nitrile ketone)(PPENK). The interaction between the PPENK and epoxy resin have been investigated by differential scanning calorimetry (DSC), FT‐IR, and dynamic mechanical analysis (DMA). The thermal and mechanical properties were characterized by thermogravimetric analysis (TGA), thermomechanical analysis (TMA), flexural, impact strength, and the critical stress intensity factor tests. The results showed that a large number of physical crosslinks formed by intermolecular and intramolecular hydrogen bonding indeed existed in the TGDDM/F‐51/PPENK blends. These interactions gave good compatibility between PPENK and epoxy resin. So that any phase separation had not been detected by DMA and scanning electron microscope (SEM). Beyond that the interaction could also be a benefit to the thermal and mechanical properties. Compared with the neat epoxy resin, the critical stress intensity factor values reached the maximum at 10‐phr PPENK, as well as the impact strength. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42938.     

Phase separation,cure kinetics,and morphology of epoxy/poly(vinyl acetate) blends

Epoxy based on diglycidyl ether of bisphenol A + 4,4′diaminodiphenylsulfone blended with poly(vinyl acetate) (PVAc) was investigated through differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA) and environmental scanning electron microscopy (ESEM). The influence of PVAc content on reaction induced phase separation, cure kinetics, morphology and dynamic‐mechanical properties of cured blends at 180°C is reported. Epoxy/PVAc blends (5, 10 and 15 wt % of PVAc content) are initially miscible but phase separate upon curing. DMTA α‐relaxations of cured blends agree with T_g results by DSC. The conversion‐time data revealed the cure reaction was slower in the blends than in the neat system, although the autocatalytic cure mechanism was not affected by the addition of PVAc. ESEM showed the cured epoxy/PVAc blends had different morphologies as a function of PVAc content: an inversion in morphology took place for blends containing 15 wt % PVAc. The changes in the blend morphology with PVAc content had a clear effect on the DMTA behavior. Inverted morphology blends had low storage modulus values and a high capability to dissipate energy at temperatures higher than the PVAc glass‐transition temperature, in contrast to the behavior of neat epoxy and blends with a low PVAc content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1507–1516, 2007     

Synthesis,thermal and mechanical behavior of a silicon/phosphorus containing epoxy resin

A liquid silicon/phosphorus containing flame retardant (DOPO–TVS) was synthesized with 9,10‐dihydro‐9‐oxa‐10‐phosphapheanthrene‐10‐oxid (DOPO) and triethoxyvinylsilane (TVS). Meanwhile, a modified epoxy resin (IPTS–EP) was prepared by grafting isocyanate propyl triethoxysilane (IPTS) to the side chain of bisphenol A epoxy resin (EP) through radical polymerization. Finally, the flame retardant (DOPO–TVS) was incorporated into the modified epoxy resin (IPTS–EP) through sol–gel reaction between the ethyoxyl of the two intermediates to obtain the silicon/phosphorus containing epoxy resin. The molecular structures of DOPO–TVS, IPTS–EP and the final modified epoxy resin were confirmed by FTIR spectra and ¹H‐NMR, ³¹P‐NMR. Thermogravimetric analysis (TGA), differential scanning calorimetry, and limiting oxygen index were conducted to explore the thermal properties and flame retardancy of the synthesized epoxy resin. The thermal behavior and flame retardancy were improved. After heating to 600°C in a tube furnace, the char residue of the modified resin containing 10 wt % DOPO–TVS displayed more stable feature compared to that of pure EP, which was observed both by visual inspection and scanning electron microscope (SEM). Moreover, the mechanical performance testing results exhibited the modified epoxy resins possessed elevated tensile properties and fracture toughness which is supported by SEM observation of the tensile fracture section. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42788.     

Synthesis,characterization of an epoxy‐terminated carbosiloxane and its application as a modifier in epoxy systems

An epoxy‐terminated carbosiloxane has been designed and synthesized as a modifier to improve toughness and stiffness of epoxy resins simultaneously. The modifier was rubbery in nature and possessed several epoxy groups. When co‐cured with a conventional epoxy precursor, diglycidyl ether of bisphenol‐A (DGEBA), it would phase separate as individual domains and thus act as a toughener. Through participating in curing reaction with its multiple epoxy groups, the crosslinking density of the system was increased and thus resulted in reinforcing of cured epoxy system. The modifier was synthesized via hydrosilylation and cohydrolysis reactions. The chemical structures of the carbosiloxane were confirmed by FTIR and ¹H NMR spectra. The cured epoxy products were characterized by dynamic mechanical thermal analysis (DMTA), thermogravimetric analysis (TGA), impact strength testing, and atomic force microscopy (AFM). POLYM. ENG. SCI., 2011. ©2011 Society of Plastics Engineers     

Effect of molecular weight and content of PDMS on morphology and properties of silicone‐modified epoxy resin

To achieve a stable blend of a bisphenol A type epoxy resin and poly(dimethylsiloxane) (PDMS), reaction between hydroxyl (OH) groups of the epoxy and silanol groups of hydroxyl‐terminated(HT) PDMS has been investigated. The chemical structures of the HTPDMS‐modified epoxies were characterized by Fourier transform infrared (FTIR) and ¹H‐ and ¹³C‐NMR spectroscopy. To allow further understanding of the influence of viscosity and content of HTPDMS on the blend morphology, four different viscosities of HTPDMS were used in three content levels. The morphologies of modified epoxy resins were observed with optical microscopy. The modified epoxies were cured with a cycloaliphatic polyamine. The morphologies of modified epoxies were investigated by using scanning electron microscopy (SEM)/energy dispersive X‐ray (EDX) technique. The cured films showed droplet in matrix morphology with different mean droplets size which was influenced by the viscosity and the content of the incorporated HTPDMS. To illustrate the effect of the morphologies of the cured samples on mechanical properties, tensile strength tests were performed. The introduction of HTPDMS into the epoxy altered the tensile behavior according to its viscosity and content. Surface properties of the cured films were evaluated by sessile drop method. The results clearly indicate that the hydrophilic surface of the epoxy turns to a hydrophobic one due to the modification with HTPDMS. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Synthesis of branched benzoxazine monomers with high molecular mass,wide processing window,and properties of corresponding polybenzoxazines

Four cyclotriphosphazene‐based benzoxazine monomers (I, II, III, and IV) with relatively high molecular weight were synthesized by a nucleophilic substitution reaction, and their chemical structures were confirmed by ¹H‐NMR and ³¹P‐NMR. A new term, oxazine value (OV, similar to epoxy value), was first proposed to explain the structure–property relationship of the cured polymers. The polymerization behaviors of the four monomers were studied by differential scanning calorimetry and Fourier transform infrared spectroscopy. The maximum exothermic peaks of the four monomers are in the range 244–248 °C. All monomers possess a wide processing window despite their high molecular weight. The thermal stability, glass‐transition temperature (T_g), and mechanical properties of each cured polymer were studied by thermogravimetric analysis and dynamic mechanical thermal analysis. The char yield at 850 °C, T_g, and storage moduli of PIV (polybenzoxazine obtained from monomer IV) are 60.0%, 218 °C, and 9.0 GPa, respectively. The surface property and humidity absorption character of the cured polybenzoxazines were also studied. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44453.     

Assessment of morphological,thermal, and viscoelastic properties of epoxy vinyl ester coating composites: Role of glass flake and mixing method

In this work, glass flake (GF)/epoxy vinyl ester resin composites were fabricated with various compositions and mixing methods. The effect of GF on thermal and mechanical behavior of these composites was investigated using different techniques such as differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), and thermogravimetric analysis (TGA). The results showed that the presence of GF in epoxy vinyl ester formulation could obviously affect the cure temperature, reaction enthalpy value, and degradation temperature. DMTA results also exhibited that the tan δ peak area decreased and storage modulus increased with increasing GF content and this effect seemed to be different depending on the initial epoxy vinyl ester compositions. The scanning electron microscopy (SEM) images showed that mixing method had a strong effect on the surface morphology, size, and distribution of glass flake. The effect of mixing method on properties of produced composite was also studied.     

Hybrid resins from polyisocyanate,vinyl ester,melamine formaldehyde and water glass: structure and properties

Abstract

Hybrid thermosets were produced from polymeric methylene diphenyl isocyanate (PMDI), styrene cross-linkable vinyl ester (VE) and water glass (WG) using melamine formaldehyde (MF) resin as additional reactive emulsifier. Vinyl ester (VE) was added to the PMDI/MF mixture in which the WG was dispersed next. The content of MF in the resin formulation was varied between 0·5 and 15 wt-%. The resulting water in oil type (W/O) emulsion (water=WG, oil=organic phase composed of PMDI+VE+MF) was cured at room temperature for 24 h followed by post-curing at T=100°C for 4 h. The chemorheology of the hybrid resins was assessed by plate/plate rheometry. Information on the morphology of the cured hybrid resins was received from scanning electron microscope (SEM), atomic force microscopic (AFM) and dynamic mechanical thermal analysis (DMTA) studies. The mechanical and fracture mechanical properties as well as the resistance to thermal degradation of the hybrid thermosets were determined and discussed.     

In situ growth of multilayered crystals in amorphous matrix: Thermal,dynamic mechanical,and morphological analysis of nylon‐6/epoxy composites

A new procedure for processing of epoxy/polyamide blend was explored via solution polymerization of ε‐caprolactam in N‐methylpyrollidone (NMP), which resulted in a suspension of nylon‐6 in solvent at room temperature. The suspension was blended with water based epoxy resin using mechanical stirring at room temperature. Several films were prepared from blend by varying the amount of nylon‐6 without curing agent. All films were fully characterized for thermal and dynamic mechanical properties using differential scanning calorimetry and dynamic mechanical analysis. The addition of nylon‐6 had a plasticizing effect on epoxy evident by decrease in glass transition temperature (T_g). The reaction between nylon‐6 and epoxy was studied using Fourier transform infrared spectroscopy by following the characteristic epoxy peak (914 cm^?1). The growth of nylon‐6 crystals in epoxy matrix lead to spherulitic multiphase morphology, which was observed under scanning electron microscope. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3319–3327, 2013     

Epoxy compositions cured with aluminosilsesquioxanes: Thermomechanical properties

The aim of this study was to verify the influence of bis(heptaphenylaluminosilsesquioxane) (AlPOSS), used as a curing agent, on the thermomechanical properties of epoxy resin. Moreover, various curing conditions were taken into account. Epoxy casts were prepared from epoxy resin based on bisphenol A cured with different amounts of bis(heptaphenylaluminosilsesquioxane). The thermomechanical properties were investigated during dynamical mechanical thermal analysis (DMTA) in two cycles of heating. The storage modulus G′ of the epoxy casts was found to be higher in comparison to the reference epoxy sample and significantly dependent on the POSS content. A correlation between the glass transition temperatures (T_g), the curing conditions and the amount of curing agents were closely related. The occurrence of the crosslinking process in epoxy matrix was proved by the FTIR spectroscopy. The structure of the epoxy casts was investigated using scanning electron microscopy (SEM). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40672.     

Improving thermal and flame‐retardant properties of epoxy resins by a new imine linkage phosphorous‐containing curing agent

A new reactive phosphorus‐containing curing agent with imine linkage called 4, 4′‐[1, 3‐phenyl‐bis(9, 10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐yl)dimethyneimino)]diphenol (2) was synthesized both via two‐pot and one‐pot procedure. The chemical structure of this curing agent was confirmed by FTIR, ¹H, ¹³C, and ³¹P NMR spectra. A series of thermosetting systems were prepared by using conventional epoxy resins (E51), 4, 4′‐diaminodiphenyl methane (DDM) and (2). Resins with different phosphorus contents were obtained by changing the DDM/(2) molar ratios. Their dynamic mechanical thermal, thermal and flame‐retardant properties were evaluated by dynamic mechanical thermal analysis (DMTA), thermogravimetric analysis (TGA), and limiting oxygen index (LOI), respectively. All samples had a single T_g, which showed that these epoxy resins were homogeneous phase. Both the two char yields under nitrogen and air atmospheres increased with increasing content of (2) and the LOI values increased from 24.5 for standard resin to 37.5 for phosphorus‐containing resin, which indicated that incorporation of (2) could impart good thermal stability and excellent flame retardancy to the conventional epoxy thermosets. POLYM. ENG. SCI., 56:441–447, 2016. © 2016 Society of Plastics Engineers     

Influence of copolymer's end groups and molecular weights on the rheological and thermomechanical properties of blends of novel thermoplastic copolymers and epoxy resins

In this paper, we present a study on the properties of epoxy resins blended with copolyethersulfones. Several copolyethersulphones were synthesized by varying the molecular weights and the end groups. The obtained thermoplastics were then mixed with diglycidyl ether of biphenol A (DGBEA) (15% wt ratio), cured with methylene bis(2,6‐diethylanine) (MDEA), and the resulting blends characterized by the use of dynamic thermal mechanical analysis (DMTA), rheometry, and fracture mechanics tests. The morphology of the blends was studied by the use of scanning electron microscopy (SEM). The different molecular weights of the copolymers had a significant effect on the rheological and thermomechanical properties of the resins, as well as the different end groups on the reaction rate and on the thermomechanical properties of the blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 250–257, 2006     

Synthesis,characterization, and properties of a novel epoxy resin containing both binaphthyl and biphenyl moieties

A new epoxy resin containing both binaphthyl and biphenyl moieties in the skeleton (BLBPE) was synthesized and confirmed by electrospray ionization mass spectroscopy, ¹H‐nuclear magnetic resonance spectroscopy, and infrared spectroscopy. To evaluate the combined influence of two moieties, one epoxy resin containing binaphthyl moiety and another containing biphenyl moiety were also synthesized, and a commercial biphenyl‐type epoxy resin (CER3000L) was introduced. Thermal properties of their cured polymers with phenol p‐xylene resins were characterized by differential scanning calorimetry, dynamic mechanical, and thermogravimetric analyses. The cured polymer obtained from BLBPE showed remarkably higher glass transition temperature and lower moisture absorption, as well as comprehensively excellent thermal stability. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Multifunctionalization of novolac epoxy resin and its influence on dielectric,thermal properties,viscoelastic, and aging behavior

In this article, novolac epoxy was functionalized using p‐hydroxybenzoic acid as pendent groups, which offered weak acidic environment and were cured with methyl etherified amino resin (HMMM). Its chemical structure was characterized by Fourier transform infrared (FT‐IR), ¹H nuclear magnetic resonance (¹H NMR) and differential scanning calorimeter (DSC). To comprehensively investigate its performance, HMMM was used as a curing agent. The modified epoxy exhibited higher storage modulus, lower thermal expansion coefficient, better moisture resistance, better resistance to degradation and lower dielectric constant. Furthermore, the aging behavior was investigated using dynamic mechanical analysis and scanning electron microscopy, which showed that the activation energy of glass transition increased after aging and cured MDEN was more difficult to age. Moreover, the relation between storage modulus and curing rate was established; the low curing rate of MDEN decreased the growth rate of storage modulus and reduced the internal stress, which was beneficial for processing. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40157.     

Effects of poly(methyl methacrylate)‐based low‐profile additives on the properties of cured unsaturated polyester resins. I. Miscibility,curing behavior,and glass‐transition temperatures

The effects of three series of self‐synthesized poly(methyl methacrylate) (PMMA)‐based low‐profile additives (LPAs), including PMMA, poly(methyl methacrylate‐co‐butyl acrylate), and poly(methyl methacrylate‐co‐butyl acrylate‐co‐maleic anhydride), with different chemical structures and MWs on the miscibility, cured‐sample morphology, curing kinetics, and glass‐transition temperatures for styrene (ST)/unsaturated polyester (UP) resin/LPA ternary systems were investigated by group contribution methods, scanning electron microscopy, differential scanning calorimetry (DSC), and dynamic mechanical analysis, respectively. Before curing at room temperature, the degree of phase separation for the ST/UP/LPA systems was generally explainable by the calculated polarity difference per unit volume between the UP resin and LPA. During curing at 110°C, the compatibility of the ST/UP/LPA systems, as revealed by cured‐sample morphology, was judged from the relative magnitude of the DSC peak reaction rate and the broadness of the peak. On the basis of Takayanagi's mechanical models, the effects of LPA on the final cure conversion and the glass‐transition temperature in the major continuous phase of ST‐crosslinked polyester for the ST/UP/LPA systems was also examined. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3369–3387, 2004     

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.     

Toughening epoxy resin with blocked isocyanate containing soft chain

A series of imidazole (MI) blocked 2,4‐toluene diisocyanate (TDI) with polyethylene glycol (PEG‐400) as soft segment (PEG‐MI‐b‐TDI) were synthesized for toughening and curing the bisphenol A type epoxy resin (E‐44). Fourier transform infrared (FTIR) spectrum indicates that the NCO groups of the isocyanate molecule are blocked with MI. For curing epoxy systems, elimination of epoxy group and the formation of urethane bonds were studied by FTIR spectroscopy. The results of mechanical property were shown that the tensile shear and impact strengths of neat MI and MI‐b‐TDI cured E‐44 are lower than those of PEG‐MI‐b‐TDI cured E‐44. Based on the scanning electron microscope studies, microstructure evolutions of the E‐44 cured by different curing agents were imaged. The mechanical, thermal, and dynamic mechanical properties were measured by universal testing machine, differential scanning calorimeter and dynamic mechanical analyzer (DMA). The toughness of E‐44 cured by PEG‐MI‐b‐TDI was effectively improved without sacrificing the tensile shear strength. Based on the DMA studies, the long soft chain of PEG brought in a noticeable lowering in the glass transition temperature (T_g). The glass transition temperature is near 165°C for the neat MI cured E‐44, which is higher than the T_gs of the other curing agents cured epoxy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41345.     

An investigation of epoxy/thermoplastic blends based on addition of a novel copoly(aryl ether nitrile) containing phthalazinone and biphenyl moieties

In this paper, a novel soluble copoly(aryl ether nitrile) containing phthalazinone and biphenyl moieties (PPBEN) was synthesized for the first time to improve the impact resistance of tetraglycidyl 4,4'‐diaminodiphenylmethane epoxy resin cured with 4,4‐diaminodiphenylsulfone. Then a series of blends were prepared via solution blending with different contents of PPBEN. The thermal and mechanical properties and the micromorphology of the cured blends were investigated by differential scanning calorimetry, dynamic mechanical analysis (DMA), parallel plate rheometry, mechanical property tests and SEM analysis, respectively. The results indicated that the incorporation of thermoplastic PPBEN delayed the epoxy curing reaction, and the crosslinking density of epoxies was also reduced. The no‐notch impact strength of the cured blend with 15% PPBEN was up to 16.7 kJ m^?2, higher by about 104% than that of pure epoxy resin without sacrificing the modulus due to a specific sea‐island structure. All the blends showed two‐phase morphology characterized by DMA and SEM. The size of the thermoplastic morphology was only 70?80 nm, much less than that of commonly used thermoplastics, due to the special segment structure of PPBEN. © 2015 Society of Chemical Industry