Synthesis,characterization, and cure of allyl and propargyl functionalized indene as a thermoset composite matrix resin

Two highly functionalized resins were synthesized by the phase transfer reaction of indene with propargyl bromide or allyl chloride in the presence of strong base. The resins consisted of a mixture of tri- and tetrafunctional indenes with 60–80% of the product being tetrafunctional. The allylated (AL) and propargylated (PL) indene resins were thermally cured without added catalysts. Both resins exhibited a broad, highly exothermic cure with a peak energy at 320°C for AL resin and 282°C for PL resin. Thermal degradation of cured AL resin was found to begin at approximately 400°C with a carbon yield of 20% of its initial weight at 1000°C. Carbon yields for cured PL resin were excellent, with 68% retention of weight at 1000°C. Unidirectional, carbon fiber composites were fabricated from the substituted indene resins. AL–carbon fiber composites gave modulus values of 126 GPa and strength values of 967 MPa, while PL–carbon fiber composites gave modulus values of 116 GPa and strength values of 935 MPa in three-point bending tests. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 475–482, 1998     

Synthesis,cure analysis,and composite properties of allylated cyclopentadiene resins

Allylated cyclopentadiene was synthesized through the phase transfer reaction of cyclopentadiene and allyl chloride in the presence of a strong base. The reaction yielded a mixture of isomers with 2 to 6 allyl groups per cyclopentadiene ring. Variations in reactant ratios changed product ratios only slightly; however, lower ratios of allyl chloride to cyclopentadiene (4:1 and 2:1) produced lower substituted products. DSC analysis of the ACP showed thermal cure without added catalyst. The total enthalpy of cure was ∼750 J/g with a peak energy at 310°C. FTIR analysis of the thermal cure showed the predominate cure mechanisms to be ene reactions and polyadditions of allyl groups with a small amount of oxidation. Partial curing (B-staging) of ACP was conducted thermally at 180 and 200°C. An increase in viscosity with time was found in each case with gelation occurring at ∼15 h and 3 h, respectively. ACP resin was also cured using various concentrations of peroxide and BF₃₀ dibutyl etherate catalysts. In all cases gelled materials were formed. ACP/carbon fiber and ACP/glass fiber composites gave flexural moduli of 165 and 42 GPa, respectively. Flexural strength values were found to be 956 MPa for ACP/carbon and 681 MPa for ACP/glass. Treatment of ACP/carbon fiber composites in boiling water or refluxing toluene had no significant effect on their mechanical properties.     

Thermal conductivity and dynamic mechanical property of glycidyl methacrylate‐grafted multiwalled carbon nanotube/epoxy composites

The well dispersed multiwalled carbon nanotube (MWCNT)/epoxy composites were prepared by functionalization of the MWCNT surfaces with glycidyl methacrylate (GMA). The morphology and thermal properties of the epoxy nanocomposites were investigated and compared with the surface characteristics of MWCNTs. GMA‐grafted MWCNTs improved the dispersion and interfacial adhesion in epoxy resin, and enhanced the network structure. The storage modulus of 3 phr GMA‐MWCNTs/epoxy composites at 50°C increased from 0.32 GPa to 2.87 GPa (enhanced by 799%) and the increased tanδ from 50.5°C to 61.7°C (increased by 11.2°C) comparing with neat epoxy resin, respectively. Furthermore, the thermal conductivity of 3 phr GMA‐MWCNTs/epoxy composite is increased by 183%, from 0.2042 W/mK (neat epoxy) to 0.5781 W/mK. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

An epoxy resin-elastomer system for filament winding

Tests characterizing an epoxy system that contains 5 percent rubber and is suitable for wet-filament winding are described. The resin is a bisphenol-A rubberized epoxy diluted with an aliphatic diglycidyl ether and cured with an aromatic amine. The viscosity and pot life were measured and the progress of cure was monitored so an optimum cure could be chosen. Mechanical tests were performed on the cured resin. The low viscosity (0.95 Pa's) and long pot life (29.3 h) make for ease of processing. A cure cycle of 1.5h at 90°C plus 2 h at 130°C gives a cured resin having a glass transition temperature of 104°C. The heat-cured material has a tensile strength of 76.1 MPa and a modulus of 2.43 GPa. Kevlar 49 composites of 60-, 65-, and 70-volume-percent fiber were prepared and tested. Results are presented and compared to two other Kevlar 49/epoxy composites.     

Mechanical properties of graphene nanoplatelet/epoxy composites

Because of their high‐specific stiffness, carbon‐filled epoxy composites can be used in structural components in fixed‐wing aircraft. Graphene nanoplatelets (GNPs) are short stacks of individual layers of graphite that are a newly developed, lower cost material that often increases the composite tensile modulus. In this work, researchers fabricated neat epoxy (EPON 862 with Curing Agent W) and 1–6 wt % GNP in epoxy composites. The cure cycle used for this aerospace epoxy resin was 2 h at 121°C followed by 2 h at 177°C. These materials were tested for tensile properties using typical macroscopic measurements. Nanoindentation was also used to determine modulus and creep compliance. These macroscopic results showed that the tensile modulus increased from 2.72 GPa for the neat epoxy to 3.36 GPa for 6 wt % (3.7 vol %) GNP in epoxy composite. The modulus results from nanoindentation followed this same trend. For loadings from 10 to 45 mN, the creep compliance for the neat epoxy and GNP/epoxy composites was similar. The GNP aspect ratio in the composite samples was confirmed to be similar to that of the as‐received material by using the percolation threshold measured from electrical resistivity measurements. Using this GNP aspect ratio, the two‐dimensional randomly oriented filler Halpin–Tsai model adjusted for platelet filler shape predicts the tensile modulus well for the GNP/epoxy composites. Per the authors' knowledge, mechanical properties and modeling for this GNP/epoxy system have never been reported in the open literature. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Curing behavior of dicyandiamide/epoxy resin system using different accelerators

Various amounts of dicyandiamide (Dicy), two grades of epoxy resins, i.e. Epiran 06 and Epikote 828, and three different accelerators including benzyl dimethyl amine (BDMA), 3-(4-chlorophenyl)-1,1-dimethyl urea (Monuron) and 2-methyl imidazole (Im) were used in curing of Dicy/epoxy resin system. Both of the used epoxy resins were based on diglycidyl ether of bisphenol A (DGEBA). The effects of type and concentration of accelerators on curing behavior were studied by differential scanning calorimetry (DSC) method in dynamic or non-isothermal mode. The optimum concentration of Dicy for curing of epoxy resins was obtained based on the glass transition temperature of the cured epoxy/Dicy formulations. The maximum glass transition temperature of 139 °C was obtained at the stoichiometric ratio of Dicy to epoxy of 0.65. The results showed that BDMA has a broader curing peak in DSC and starts the cure reaction earlier than the others. However, Monuron has a narrow curing reaction peak with good cure latency. The tensile properties of Dicy-cured Epiran 06 and Epikote 828 epoxy resins reinforced with chopped strand mat showed that these two epoxy resins have similar mechanical properties. For composites based on the Epiran 06 and Epikote 828 reinforced with 40 wt % glass chopped strand mat, tensile strength and modulus were 156 and 153.4 MPa and 11.6 and 12.4 GPa, respectively.     

Characterization of a rigid silicone resin

Silicone resins have been used as binders for ceramic frit coatings and can withstand temperatures of 650°C to 1260°C. Conceptually, silicone resins can potentially be used as matrices for high temperature fiber‐reinforced composites. The mechanical and thermal properties of a commercially available silicone resin, Dow Corning® 6‐2230, were characterized. Neat 6‐2230 resin was found to have inferior room temperature mechanical properties such as flexural, tensile and fracture properties when compared to epoxy. The room temperature flexural properties and short beam shear strength of the silicone/glass composites were also found to be lower than those of epoxy/glass composite with similar glass content. However, the silicone resin had better elevated temperature properties. At an elevated temperature of 316°C, the retentions of flexural modulus and strength were 80% and 40% respectively of room temperature values; these were superior to those of phenolic/glass. Unlike the carbon‐based resins, the drop in flexural properties of the silicon/glass laminates with temperature leveled off with increase in temperature beyond 250°C. The resin weight loss at 316°C in 100 cm³/min of flowing air was small compared to other carbon‐based resins such as PMR‐15 and LaRC TPI. Only Avimid‐N appeared comparable to Dow Corning® 6‐2230.     

A novel rapid cure epoxy resin with internal mold release

Mold preparation, material layup, and cure times for thermoset-based composites often limit their use in high-volume applications. As such, new rapid cure epoxy resins are being developed to achieve a complete cycle time within 3 min. In this research, calorimetry and rheometry are used to examine and model two novel rapid cure epoxy resin systems with internal mold release. The rapid cure epoxy resins followed an autocatalytic cure kinetic and William–Landel–Ferry diffusion model. The rapid cure epoxy resin was shown to achieve 94% cure in 2 min at 150°C. However, adding an additional 2.5 wt% internal mold release hindered the first step of the reaction, which delayed the second reaction step since the final degrees of cure were similar. Furthermore, the resin viscosity followed a modified William–Landel–Ferry equation and at 120°C could maintain a viscosity below 5 Pa s for 4.1 min. These models provided valuable insight into the range of processing conditions these novel resins could experience during impregnation and molding processes.     

Study on BMI modified allyl‐functional novolac resin/silica cloth composites: Effect of allylation degree on thermal and mechanical properties

A series of allyl‐functional novolac resin with various allylation degree, from 32.4 to 114.6%, were synthesized and then blended reactively with 4,4′‐bismaleimide biphenyl methane (BMI) at a weight ratio of 2.50:1 to get BMI‐modified allyl‐functional novolac (BMAN) resins. BMAN resins were used as matrix resin to fabricate BMAN/Silica cloth composites by compression molding process. Heat‐resistant properties of the composites were evaluated by means of dynamic mechanical analysis. The results indicated that thermal resistance of the composites increased as allylation degree of BMAN resins increased. Mechanical properties of the composites, including interlaminar shear strength (ILSS) and flexural strength at room temperature and 300°C, were determined, and the results showed that with increase in allylation degree of matrices the ILSS and flexural strength values of composites at room temperature decreased, but the values of ILSS and flexural strength at 300°C increased. Scanning electron microscope morphology analysis of fracture surface for composites revealed that tough interphase was responsible for the better mechanical properties of the composites based on lower allylation degree resins. POLYM. COMPOS., 28:180–185, 2007. © 2007 Society of Plastics Engineers     

Thermosetting matrices for composite materials based on allyl/propagryl substituted novolac resins

A new type of modified thermoset resins was synthesized by Williamson reaction from novolac resin and a mixture of allyl and propargyl chlorides of the different ratios with total allyl/propargyl substitution 50 %. The compositions of the resins were defined by nuclear magnetic resonance (¹H NMR) spectroscopy, and the dependence of the cured material properties on the composition was established. An increase of a propargyl content resulted in char yield raise, and the maximum value had been found for propargylated resin which was 60 %. By differential scanning calorimetry (DSC) analysis of the curing process, it was demonstrated that exothermic enthalpy could be adjusted by varying the content of propargyl and allyl groups in the resin. It was shown that the resin substituted with allyl only ether could not be cured without decomposition, but an introduction of propargyl groups in allyl ether-modified resin allowed to obtain cured samples and thus to develop a new type of thermosetting resins.     

Eugenol‐Derived Bismaleimide High Performance Resins and Composites Using Diisocyanate as Property Modifier

A new kind of high performance bismaleimide resin with good processability and improved toughness is synthesized by chemical modification of 4,4′‐bismaleimidodiphenylmethane (BMI) by eugenol (EG) and different contents of 4,4′‐diphenylmethane diisocyanate (MDI). MDI‐EG‐BMI resins exhibit good thermal stability for its 5% weight loss temperatures around 300 °C and its residue of 41.61% at 900 °C, which are much higher than those of EG‐BMI resin. Then, the carbon fiber‐reinforced MDI‐EG‐BMI composites are fabricated. The mechanical properties of the composites matrixed by MDI‐EG‐BMI resins are better than those by EG‐BMI resin. For carbon/MDI‐EG‐BMI composites, their glass transition temperatures are higher than 300 °C, and their flexural strength, moduli, and toughness are maintained at a range of 217.47–404.36 MPa, 35.12–48.49 GPa, and 1.16–2.63 MJ m^?3 respectively; with the contents increasing of MDI in the resin formulation, the flexural properties first increase then decrease; comprehensively the composite with 30 wt% MDI has the best mechanical and thermal properties.     

Synthesis and characterization of chlorinated soy oil based epoxy resin/glass fiber composites

Composites with good toughness properties were prepared from chemically modified soy epoxy resin and glass fiber without additional petroleum based toughening agent. Chlorinated soy epoxy (CSE) resin was prepared from soybean oil. The CSE was characterised by spectral, and titration method. The prepared CSE was blended with commercial epoxy resin in different ratios and cured at 85°C for 3 h, and post cured at 225°C for 2 h using m‐phenylene diamine (MPDA) as curing agent. The cure temperatures of epoxy/CSE/MPDA with different compositions were found to be in the range of (151.2–187.5°C). The composite laminates were fabricated using epoxy /CSE/MPDA‐glass fiber at different compositions. The mechanical properties such as tensile strength (248–299 MPa), tensile modulus (2.4–3.4 GPa), flexural strength (346–379 MPa), flexural modulus (6.3–7.8 GPa) and impact strength (29.7–34.2) were determined. The impact strength increased with the increase in the CSE content. The interlaminor fracture toughness (G_IC) values also increased from 0.6953 KJ/m² for neat epoxy resin to 0.9514 KJ/m² for 15%CSE epoxy‐modified system. Thermogravimetric studies reveal that the thermal stability of the neat epoxy resin was decreased by incorporation of CSE. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

碳纤维湿法缠绕用环氧树脂基体研究

以TDE-85树脂和AFG-90树脂为主体树脂,混合芳香胺为固化剂,研究了一种适合于碳纤维复合材料湿法缠绕成型的树脂配方。结果表明,该树脂的黏度低(＜550 mPa·s)、适用期长,其浇铸体具有优异的力学性能,其拉伸强度为107 MPa,拉伸模量为4．09 GPa,弯曲强度为161 MPa,弯曲模量为3．88 GPa,断裂伸长率超过6%。用其制备的T-700碳纤维缠绕复合材料界面粘接好,NOL环层间剪切强度达到66．8 MPa,拉伸强度达到2．44 GPa。     

Thermally reversible and self‐healing novolac epoxy resins based on Diels–Alder chemistry

The modified novolac epoxy resins with furan pendant groups were prepared by novolac epoxy resin and furfuryl alcohol and then crosslinked by bifunctional maleimide via Diels–Alder (DA) chemistry to obtain the thermally reversible and self‐healing novolac epoxy resins. The as‐prepared crosslinked novolac epoxy resins were characterized by FT‐IR, NMR, TGA, and DMA. The results indicate that the novel crosslinked novolac epoxy resins present higher storage modulus (2.37 GPa at 30°C) and excellent thermal stability (348°C at 5% mass loss). Furthermore, the thermal reversible and self‐healing properties were studied in detail by DSC, SEM, thermal re‐solution, and gel–solution–gel transition experiments. All the results reveal that the crosslinked novolac epoxy resins based on DA reaction can be used as smart material for the practical application of electronic packaging and structural materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42167.     

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.     

Preparation and properties of biocomposites composed of glycerol‐based epoxy resins,tannic acid,and wood flour

After polyglycerol polyglycidyl ether (PGPE) and glycerol polyglycidyl ether (GPE) were mixed with tannic acid (TA) in ethanol and without solvent at epoxy/hydroxyl ratio 1/1, the obtained GPE‐TA and PGPE‐TA solutions were mixed with wood flour (WF), prepolymerized at 50°C, and subsequently compressed at 160°C for 3 h to give GPE‐TA/WF and PGPE‐TA/WF biocomposites with WF content 50–70 wt %, respectively. The storage moduli of the biocomposites in the rubbery state at more than 80°C were much higher than that of the control cured resins. The PGPE‐TA/WF composites had higher tensile modulus and rather lower tensile strength than PGPE‐TA. On the other hand, both the tensile modulus and strength of GPE‐TA/WF were much higher than those of GPE‐TA (2.4 GPa and 37 MPa). Those values of GPE‐TA/WF increased with WF content, became maximal values (5.1 GPa and 51 MPa) at WF content 60 wt %, and were lowered at 70 wt %. FE‐SEM analysis of the fractured surface of the biocomposites revealed that WF is tightly incorporated into the crosslinked epoxy resins. As a result of optimization of the epoxy/hydroxyl molar ratio for GPE‐TA/WF composite with WF content 60 wt %, the composite prepared at the ratio of 1.0/0.8 showed the highest tensile modulus and strength. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Novel thermosetting resins for SMC applications from linseed oil: Synthesis,characterization, and properties

New thermosetting resins for applications of sheet‐molding compounds (SMCs) were successfully synthesized from linseed oil, which is the most molecularly unsaturated of all plant oils. The carbon–carbon double bonds were opened by epoxidation, followed by acrylation, and then maleinization, which provided more crosslink sites and added acid functionality on the triglyceride molecules to develop thickening. Dynamic mechanical analysis showed that the storage modulus of these new polymers was approximately 2.5 GPa at 30°C, and the glass‐transition temperature was above 100°C. During maturation the resins reached a molding viscosity quickly and stayed stable. Mechanical tests showed a flexural strength of 100 MPa and a flexural modulus of 2.8 GPa. Thermogravimetric analysis showed a single degradation ranging from 300°C–480°C, which was a result of the carbonization of the crosslinked network. These bio‐based resins are promising as replacements of some petroleum‐based resins in the SMC industry. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Thermal characterization of carbon‐nanofiber‐reinforced tetraglycidyl‐4,4′‐diaminodiphenylmethane/4,4′‐diaminodiphenylsulfone epoxy composites

The thermal properties of carbon nanofibers (CNF)/epoxy composites, composed of tetraglycidyl‐4,4′‐diaminodiphenylmethane (TGDDM) resin and 4,4′‐diaminodiphenylsulfone (DDS) as a curing agent, were investigated with differential scanning calorimetry (DSC), thermogravimetric analysis, and dynamic mechanical thermal analysis. DSC results showed that the presence of CNF had no pronounced influence on the heat of the cure reaction. However, the incorporation of CNF slightly improved the thermal stability of the epoxy. Furthermore, the storage modulus of the TGDDM/DDS epoxy was significantly enhanced, whereas the glass‐transition temperature was not significantly affected, upon the incorporation of CNFs. The storage modulus of 5 wt % CNF/epoxy composites at 25°C was increased by 35% in comparison with that of the pure epoxy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 295–298, 2006     

Interlaminar shear properties of graphite fiber,high-performance resin composites

Shear properties of laminates consisting of graphite fiber (Celion 6000, Celion 3000, and T-300) and several resins (epoxy, hot melt-bismaleimide, solvent bismaleimide, polyimide, and polystyrylpyridine (PSP)) were measured using the short-beam test. The interlaminar shear strength of epoxy composites was hightest. All other resin composites showed considerably lower shear properties. The shear strengths deereased with temperature, with the loss up to 100°C being more pronounced. The PSP composites did not show a loss in strength in the temperature range investigated (room temperature to 250°C). Boiling the composite samples in water for 24 h resuled in negligible reduction in shear strength in all cases. The interlaminar shear properties depended on the fiberresin interfacial bond, the wetting characteristics of the resin, and the resin meechanical properties. Attempts were made to determine to what extent each of these factors controlled the shear properties of the composites studies. Thus, the interfacial bond between the resin and the single fiber was determined. Results showed that the lower shear strength of polyimide, bisimides and PSP composites, as compared to epoxy resin composites, seemed to be due to their corresponding low interfacial bond strengths. The subsequent decrease in shear strength with temperature appeared to be directly correlated to the decrease in bond strength. The wettability of carbon fiber tow with all these resins was also determined. The small variations in wetting characteristics of the resin did not seem to justify the rather large differences in shear-strength properties observed.     

Investigation of readily processable thermoplastic-toughened thermosets. II. Epoxy toughened using a reactive solvent approach

The fracture toughness of epoxy thermosets was increased by up to 220% using very low-molecular-weight (∼ 1000 g/mol) imide thermoplastic. The objective was to produce a low-viscosity prepolymer that could be easily autoclave-processed to give a tough thermoset. Here, an homogenous epoxy prepolymer was prepared by first synthesizing very low-molecular-weight linear aromatic imide (∼ 1000 g/mol) directly in a liquid allyl phenol reactive solvent, followed by dissolution of the epoxy (Epon® 825) and the cure agent (DDS) directly in the thermoplastic solution. The allyl phenol both cures into the epoxy network, through phenol functional groups, and accelerates the cure. The viscosity of the pure epoxy was 1.4 Pa · S at 30°C. The prepolymer formulations ranged from ∼ 5–33 Pa · S at 30°C, but all reduced to less than 1 Pa · S at 90°C. The onset of cure is well above 90°C so the prepolymer viscosity is within the range for autoclave processing. The cured resin plaques were not transparent, but phase-separated domains were not found by scanning electron microscopy, indicating that the domain size is below the detection limit of the instrument. The reactive solvent causes a decrease in both the T_g and the high temperature modulus of the thermoset. Introduction of the thermoplastic results in partial recovery of the T_g and modulus. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 935–942, 1998