Thermosetting bismaleimide resins generating covalent and multiple hydrogen bonds

Prepolymerizations of 4,4′‐bismaleimidodiphenylmethane (BMI), diallyl isocyanurate (DAIC), and melamine (ML) at 160–170°C and subsequent compression molding at 200–280°C yielded cured BMI/DAIC/ML resins with feed molar ratios of 4/1/1, 3/1/1, and 2/1/1 (BMI‐DAIC‐ML411, 311, and 211). Similarly, cured BMI/DAIC 1/1 and BMI/ML 3/1 resins (BMI‐DAIC11 and BMI‐ML31) were prepared. The FT‐IR analysis revealed that the maleimide and allyl groups were almost consumed for all the cured resins, and the hydrogen bonding interaction became stronger with decreasing BMI contents for BMI‐DAIC‐MLs. Based on the cured structures elucidated from the FT‐IR result, the numbers of multiple hydrogen bonds and cross‐linking covalent bonds (N_MHB and N_CB), and total cross‐linking bond energy (E_TB) were evaluated to be 0, 7.92, and 618 for BMI‐DAIC‐ML411, 0.71, 7.81, and 627 for BMI‐DAIC‐ML311, and 0.95 mol kg^?1, 7.61 mol kg^?1, and 617 kcal kg^?1 for BMI‐DAIC‐ML211, respectively. A higher order of glass transition and 5% weight loss temperatures for BMI‐DAIC‐MLs was 411 > 311 > 211 in accordance with a higher order of N_CB. BMI‐DAIC‐MLs displayed a weak tan δ peak at 70–150°C due to dissociation of the hydrogen bonds. The flexural strength and modulus of BMI‐DAIC‐ML311 were higher than those of BMI‐DAIC‐ML411 in accordance with the difference of E_TB. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43121.     

Replacement of styrene with acrylated epoxidized soybean oil in an unsaturated polyester resin from propylene glycol,isophthalic acid,and maleic anhydride

Commercial unsaturated polyester (UPE) resins typically contain a high amount of volatile toxic styrene. A non‐volatile acrylated epoxidized soybean oil (AESO) was found to be an excellent replacement of styrene in a commercially available UPE resin [designated as Styrene‐(PG‐IPA‐MA)] that is derived from propylene glycol (PG), isophthalic acid (IPA), and maleic anhydride (MA) in terms of the mechanical properties of the resulting kenaf fiber‐reinforced composites. The AESO‐(PG‐IPA‐MA) resins had low viscosity and long pot life below 70°C for a typical fiber‐reinforced composite application. AESO and PG‐IPA‐MA were not able to form a strong polymer matrix individually for fiber‐reinforced composites. However, a combination of AESO and PG‐IPA‐MA saw strong synergistic effects between them. The flexural, tensile, and water absorption properties of kenaf fiber‐reinforced composites made from AESO‐(PG‐IPA‐MA) resins were comparable with or even superior to those from the Styrene‐(PG‐IPA‐MA) resin. The AESO/(PG‐IPA‐MA) weight ratio was investigated for maximizing the mechanical properties of the kenaf fiber‐reinforced composites. The curing mechanism of the AESO‐(PG‐IPA‐MA) resins is discussed in detail. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43052.     

Selective preparation of oligomeric naphthylene ether and its applications to epoxy resin for silicon carbide power semiconductor device materials

In this study, a novel method for selective synthesis of naphthylene ether trimers by self‐condensation of 2,7‐dihydroxynaphthalene in the presence of catalytic amount of potassium hydroxide was reported. An epoxy resin from the trimers was prepared and properties of the cured epoxy resin were examined. The cured resin showed not only good physical thermal stability, such as high glass transition temperature and low thermal expansion coefficient, but also good chemical thermal stability like high thermal decomposition temperature. Additionally, low moisture absorption of the cured resin was confirmed. From these results, the newly prepared epoxy resin with naphthylene ether skeletons was considered to be suitable for advanced applications such as silicon carbide power semiconductor device. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43339.     

Flexible aliphatic poly(isocyanurate–oxazolidone) resins based on poly(ethylene glycol) diglycidyl ether and 4,4′‐methylene dicyclohexyl diisocyanate

New flexible aliphatic oxazolidone‐isocyanurate networks (AISOX) are obtained by reacting a low molecular weight diisocyanate (4,4′‐methylene dicyclohexyl diisocyanate, H₁₂MDI) and a macro‐diepoxyde (poly(ethylene glycol) diglycidyl ether, M_n = 526, PEGDGE) in different molar ratio. The curing reaction, carried out from 25 °C to 200 °C, is studied by using DSC and FTIR. The effect of the molar ratio of the two monomers on thermal and mechanical properties of AISOX resins is investigated by DSC, thermogravimetric analysis, stress?strain measurements and optical microscopy. Independently from the feed composition, it is observed that the reaction steps are: (i) partial hydrolysis of isocyanate caused by water traces, (ii) incomplete trimerization of isocyanate to give isocyanurate, and (iii) formation of oxazolidone and complete conversion of isocyanate. At the highest concentration of the soft macrodiepoxyde (PEGDGE), the AISOX resin is in the rubbery state at room temperature and shows an elastomeric behavior. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43404.     

Influence of the introduction of flexible alkyl chains on the thermal behavior and mechanical properties of mesogenic epoxy thermosets

A mesogenic epoxy resin (DGETAM) was cured with a series of curing agents having different lengths of long alkyl chain (nBAB, n = 4, 8, 12). Properties of the curings were compared with those of the DGEBA cured with the same curing agents revealing the achievement of a balance between certain levels of thermal properties and excellent mechanical properties. Moreover, some curing systems were prepared with twin mesogenic type epoxy resins (DGEnMA, n = 4, 6, 8, 10, 12) having different lengths of alkyl chain as a flexible spacer and the same curing agents (n′BABs). Combinations of the same concentrations of chemical structures in the basic units of the network structure were applied, and the thermal and mechanical properties of their curing systems were investigated. The fracture energy of each system increased considerably with the increase of the alkyl chain length that adjoins the two mesogenic groups in the epoxy resins. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44244.     

Synthesis and architecture study of a reactive polybutadiene polyamine as a toughening agent for epoxy resin

In this study, a novel reactive toughener for the epoxy resin was developed and compared with traditional hydroxyl‐terminated polybutadiene (HTPB). For this purpose, the highly reactive aliphatic amine‐terminated polybutadiene (ATPB) was synthesized at ambient conditions by nucleophilic substitution amination. The characterizations of the product were provided by Fourier transform infrared and ¹H NMR spectroscopy. According to the mechanical test results, incorporation of ATPB into epoxy networks can significantly toughen the epoxy matrix. The addition of 10 phr ATPB increased the critical stress intensity factor (K_IC) and critical strain energy release rate (G_IC) of the epoxy from 0.85 to 2.16 MPa m^1/2 and from 0.38 to 3.02 kJ m^?2, respectively. Furthermore, unlike HTPB, the presence of the ATPB did not deteriorate the tensile strength of the matrix. The toughening and failure mechanisms were discussed based on the epoxy network morphological characteristics. The reduction in cross‐linking density and glass transition temperature of the epoxy system upon modification with liquid rubbers was confirmed by dynamic mechanical analysis. This article opens up the possibility of utilizing reactive flexible diamines with polybutadiene backbone as effective toughening agents for thermoset polymers. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44061.     

Low temperature cure of epoxy thermosets attaining high Tg using a uniform microwave field

It is demonstrated for the first time that an epoxy thermoset resin can be cured at temperatures well below its T_g∞. This study compared the use of a uniform variable frequency microwave (VFM) field to standard oven curing at temperatures above and below T_g∞. Using T_g, tan δ, modulus, and FTIR measurements, it is shown that the reaction of BFDGE with MDA to attain a product with T_g∞ of 133 °C is achieved by VFM at temperatures from 100 to 140 °C; in contrast, the thermal cure normally requires 170 °C to attain the same T_g∞ and the same extent of cure. By following the pregel cure reaction with ¹³C‐NMR spectroscopy, it was determined that the lower cure temperatures of VFM cure predominately lead to chain extension and smaller amounts of crosslinking compared to the thermal cure. To explain these results, it is suggested that, after gelation, with VFM cure there is higher mobility from dipole rotations that continues the cure to completion without vitrification. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44222.     

Tough hyperbranched epoxy/poly(amido‐amine) modified bentonite thermosetting nanocomposites

A tough and highly flexible hyperbranched epoxy and poly(amido‐amine) modified bentonite based thermosetting nanocomposite was demonstrated. The FTIR, XRD, and TGA analyses confirmed the modification of bentonite. The formation of partially exfoliated structure of the nanocomposite with good physicochemical interactions among the hyperbranched epoxy, poly(amido‐amine) hardener and modified clay was investigated by the FTIR, XRD, SEM, and TEM analyses. Significant improvements of 750% toughness, 300% elongation at break, 50% tensile strength, 300% modulus, and 250% adhesive strength of the pristine epoxy were achieved by the formation of nanocomposites with 3 wt % of modified clay. The experimental modulus values of the nanocomposites were compared with three theoretical models to account the interactions between filler and matrix. Thus, the studied epoxy nanocomposite has great potential to be used as an advanced epoxy thermoset. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40327.     

Reinforcing thermosets using crystalline desoxyanisoin structures

This article presents results on the potential of using crystalline flame retardants for thermoset reinforcement. The approach involves introducing reinforcement in thermosetting polymers through low molecular weight crystallizable additives. Thermally induced phase separation (TIPS) and crystallization of desoxyanisoin in diglycidylether of bisphenol‐A (DGEBA) epoxy monomer were investigated. Small angle light scattering and polarized optical microscopy were utilized to monitor phase separation and the crystallization of desoxyanisoin in DGEBA at different concentrations. Reaction induced phase separation (RIPS) with polyetheramine was carried out under isothermal and temperature gradient curing conditions. Altering the cure schedule resulted in a rich range of morphologies due to the competition between TIPS and RIPS. During isothermal cure, straight fiber‐like anisotropic crystals on a centimeter length scale developed. In contrast, thermal gradients frustrated the crystal growth and resulted in complex and rich morphologies. Desoxyanisoin provided marginal epoxy thermoset reinforcement at 10 vol %. However, the additive did not increase the thermoset flammability retardancy. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39853.     

Fire‐retardant hybrid thermosetting resins from unsaturated polyesters and polysilazanes

This introduces an organic–inorganic thermosetting hybrid resin system based on unsaturated polyester and polysilazanes. It shows the chemical modification of unsaturated polyester structures by end capping to enable the combination of both components. In general, halogen‐free unsaturated polyesters are not fire‐retardant and have to be equipped with additives. Fillers and intumescent additives are preponderantly used in today's fire‐retardant formulations. In contrast to these fire‐retardants, polysilazanes act as ceramizing agents. Polysilazanes are suitable fire‐retardants for resin transfer molding due to their low viscosity. Both burning behavior and glass transition temperature (T_g) are investigated as important application properties. In contrast to state‐of‐the‐art fire‐retardant formulations polysilazane‐based thermosetting hybrid resins burn with high intensity and fast extinction. Therefore, total heat and smoke emission is decreased. The formation of ceramic structures during burning results in high residual mechanical properties and a low mass loss. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40375.