The effect of chain packing on the thermal and dynamic mechanical behaviour of liquid‐crystalline epoxy thermosets

Liquid‐crystalline thermosets (LCTs) have received considerable attention since they exhibit many interesting properties. However, some aspects concerning LCTs are still unexplored. In particular, the structure–property relationships, as far as the organization of liquid‐crystalline (LC) domains in cured thermosets is concerned, have not been fully elucidated yet. We investigated the effect of the presence of a nematic mesophase on the thermal and dynamic mechanical behaviour of p‐(2,3‐epoxypropoxy)phenyl‐p‐(2,3‐epoxypropoxy)benzoate cured with 2,4‐diaminotoluene. Fourier transform infrared spectral analysis showed that epoxy group conversion was complete in both LC and isotropic (ISO) systems; moreover, a greater amount of intermolecular hydrogen bonding in the LC material was found. Thermogravimetric analysis evidenced similar thermal stability for the two systems, but a kinetic analysis of the data showed that the degradation process is more complex for the LC sample, and is characterized by higher activation energy. Dynamic mechanical thermal analysis (DMTA) showed lower glass transition temperature values for the LC system. Solid‐state NMR analysis evidenced lower paramagnetic oxygen absorption for this system. DMTA results show that the ISO material possesses a larger number of physical crosslinks, which act as extra constraints on the molecular motions. In the case of the LCT, the formation of a locally more dense structure is postulated, where the presence of more extended macromolecular segments leads to a smaller number of physical crosslinks, as also confirmed by solid‐state NMR analysis. A more compact molecular packing also leads to an increase of the activation energies of the thermal degradation process of the LC system. Copyright © 2010 Society of Chemical Industry     

Molecular dynamics study on thermal and mechanical properties of AOO modified DGEBA-anhydride insulating materials for high voltage GIS

Increases in rated voltage and power density of high voltage gas insulated switchgears (GIS) impose stringent requirements on the diglycidyl ether of bisphenol A (DGEBA)-anhydride thermoset, which is widely used as insulation materials for high GIS, for higher mechanical and heat-resistant properties. In this paper, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (AOO) was copolymerized with DGEBA -anhydride system to increase the mechanical and thermal properties of the thermosets. Based on the molecular dynamics simulation method, the coefficient of thermal expansion, glass transition temperature (T_g), and modulus of AOO copolymer-modified DGEBA-anhydride thermosets were calculated. The AOO copolymer-modified DGEBA-anhydride thermosets specimens were further experimentally prepared and subjected to differential scanning calorimeter test, TGA test, tensile bending test, and dielectric test. The results of simulation and experiment simultaneously indicated that the T_g and modulus of the DGEBA-anhydride thermoset are enhanced after AOO modification. This is mainly due to the decrease in free volume percentage and mean square displacement of the epoxy cross-linked network structure after the introduction of AOO molecules, which makes the structure more compact and the cross-link density increased. Additionally, the dielectric performances of the thermoset was enhanced by AOO. The excellent thermal, mechanical and dielectric properties of AOO modified DGEBA-anhydride thermoset make it a promising application in the field of high voltage GIS.     

Synthesis and improved mechanical properties of twin-mesogenic epoxy thermosets using siloxane spacers with different lengths

A series of twin-mesogenic epoxy resins with siloxane (di-, tri-, and tetra-siloxane) chain spacers of different lengths were successfully synthesized. Results showed that the melting point of the twin-mesogenic epoxy monomers decrease by more than 50 °C due to the change of siloxane spacer length. In particular, the tri- and tetra-incorporated siloxane twin-mesogenic epoxy monomers showed a liquid crystalline (LC) phase below 100 °C during the cooling process. Epoxy thermosets with isotropic and smectic (S_m) LC phases were then prepared using an aromatic amine and the dependence on curing temperature was investigated. Furthermore, the relationship between the ordered network chain structure and mechanical properties was investigated. Results were compared with isotropic and S_m LC phases. The tensile strain and fracture energy in the S_m type LC thermosets increased without a decrease in the tensile modulus, and this occurred in all systems irrespective of siloxane spacer length. The maximum value of the fracture energy (283 kJ m⁻²) reached by LC thermosets with increased spacer lengths was twice as large as that using the alkyl chain spacer (144 kJ m⁻²). © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47891.     

Thermal degradation of LC epoxy thermosets

A novel liquid crystalline (LC) epoxy monomer was cured with different types of hardeners. The thermal‐degradation properties of cured thermosets were evaluated by thermogravimetric (TG) analysis. Several widely used kinetic models were reviewed and used to fit the TG data. The experimental results showed that the methods from one constant heating rate are insensitive to the magnitude of reaction order n. The Kissinger and Osawa methods from multiple processes would give more confident kinetic parameters in these observed systems. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1514–1521, 2000     

Improving glass transition temperature of unsaturated polyester thermosets: Conventional unsaturated polyester resins

Highly crosslinkable unsaturated polyester resins (UPR) have attracted many interests in the application as reinforced matrix materials. Here, we present a systematical study of the influence of different curing conditions and styrene concentrations on resin viscosity and dynamic-mechanical properties of the thermoset. The pure maleic Palapreg® P18-03 was selected as model UPR because of its broad industrial use. By applying newly developed thermal curing profiles (without thermal initiators) and by raising the styrene content, the T_g of the network could be increased up to 206/215°C (1/10 Hz). For the first time, a fast curable UPR based on propylene glycol and neopentyl glycol with a T_g of up to 215°C is described. A partial substitution of problematic styrene with methylmethacrylate, tert-butylacrylate, and maleic anhydride (MA) was studied as well. MA leads to significantly improved resin reactivity. A resin containing 42 wt% styrene and 8 wt% MA yields thermosets with remarkably improved mechanical properties and with a narrower glass transition range compared to the original P18-03.     

Noncovalent functionalization of carbon nanotubes using branched random copolymer for improvement of thermal conductivity and mechanical properties of epoxy thermosets

A branched random copolymer, poly[(hydroxyethyl acrylate)‐r‐(N‐vinylcarbazole)] (BPHNV), was synthesized through a facile one‐pot free radical polymerization with hydroxyethyl acrylate and N‐vinylcarbazole monomers, using 4‐vinylmethylmercaptan as the chain transfer agent. BPHNV was employed to noncovalently modify multiwall carbon nanotubes (MWCNTs) by π–π interaction. The as‐modified MWCNTs were then incorporated into epoxy resin to improve the thermal conductivity and mechanical properties of epoxy thermosets. The results suggest that, due to both the conjugation structure and the epoxy‐philic component, BPHNV could form a polymer layer on the wall of MWCNTs and inhibit entanglement, helping the uniform dispersion of MWCNTs in epoxy matrix. Owing to the unprecedented thermal conductivity of MWCNTs and the enhancement in the interfacial interaction between fillers and matrix, the thermal conductivity of epoxy/MWCNTs/BPHNV composites increases by 78% at extremely low filler loadings, while the electrical resistivity is still maintained on account of the insulating polymer layer. Meanwhile, the mechanical properties and glass transition temperature (T_g) of the thermosets are elevated effectively, with no significant decrease occurring to the modulus. The addition of as little as 0.1 wt% of MWCNTs decorated with 1.0 wt% of BPHNV to an epoxy matrix affords a great increase of 130% in impact strength for the epoxy thermosets, as well as an increase of over 13 °C in T_g. © 2018 Society of Chemical Industry     

Morphology and thermal properties of liquid crystal p‐PAEB/styrene copolymer

The homopolymer of unsaturated liquid crystal (LC) monomer for p‐phenylene di {4‐[2‐(allyloxy) ethoxy] benzoate} (p‐PAEB), and copolymer poly (p‐PAEB/St) of p‐PAEB with styrene (St) have been synthesized. The LC behavior and thermal properties of p‐PAEB and poly(p‐PAEB/St) have been studied by Polarizing Optical Microscopic (POM), Differential Scanning Calorimetry, X‐Ray Diffractometer (XRD), and Torsional Braid Analysis (TBA). The results demonstrate that LC phase texture and phase transition temperature of copolymers are affected by the composition of LC units in copolymers. The POM and XRD reveal that p‐PAEB has a smectic phase structure; the copolymer of p‐PAEB with styrene reveal deformed focal conics texture of smectic phase. The phase transition temperature range of p‐PAEB is 120.5–191.5°C, but the homopolymer of p‐PAEB has a broad LC temperature range from 77 to 170°C. The LC temperature range of poly(p‐PAEB/St) is broadened with increased content of p‐PAEB. The dynamic mechanical properties of LC polymer networks were investigated with TBA. The results indicate that the peak temperature of maximal mechanical loss is 114°C and is decreased with the addition of styrene © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5731–5736, 2006     

A novel approach to the tailoring of polymers for advanced composites and optical applications,involving the synthesis of liquid crystalline epoxy resins

The authors describe the features of liquid crystalline epoxy resins having both high and low crosslinking densities. These materials seem to be very promising as matrices in advanced composites and in optical and electro-optical applications because of their peculiar properties. The importance of factors like molecular rigidity, nature of the curing agent, and curing temperature for the development of such properties are analyzed. The authors showed that amines produce thermosets having high T_gs and high fracture toughness. In particular, the enhancement of this last parameter is very promising if a new generation of matrices is to be sought for manufacturing composites. In the case of acids as curing agents, thermosets having lower T_gs and more ordered mesophases can be obtained. In this case, LC elastomers can be prepared that can find applications in the optical industry as waveguides or electro-optical devices.     

Structure-property relationships of controlled epoxy networks with quantified levels of excess epoxy etherification

Epoxy thermosets are commonly formulated with an excess of epoxy resin to ensure complete reaction of co-reactive hardeners and to optimize performance. However, the degree to which the reaction of the excess epoxy resin contributes to the thermal and mechanical properties of the thermoset is incompletely understood. In this report, the preparation of controlled epoxy thermosets containing varying amounts of excess epoxy resin having essentially complete excess epoxy conversion is described. The extent of conversion was determined using a solid-state ¹³C NMR method with enhanced resolution due to solvent swelling of the thermosets. This etherification reaction increases the crosslink density of the epoxy thermosets but uniquely affects the thermal and mechanical properties of the materials. Significant property differences observed with respect to analogous thermosets made by varying crosslink density using different extender/hardener ratios are the sensitivity of T_g to the crosslink density and enhanced fracture toughness and tensile yielding with reduced bulk density.     

Enhancement of dielectric constants of epoxy thermosets via a fine dispersion of barium titanate nanoparticles

In this study, we examined a facile approach for achieving a fine dispersion of barium titanate (BT) nanoparticles (NPs) in epoxy thermosets. First, the surfaces of BT NPs were modified with poly(ε‐caprolactone) (PCL) via a surface‐initiated ring‐opening polymerization approach. We found that the PCL‐grafted BT NPs were easily dispersed in epoxy thermosets. The fine dispersion of the PCL‐grafted BT NPs in the epoxy thermosets was evidenced by transmission electron microscopy and dynamic mechanical thermal analysis. We found that the organic–inorganic nanocomposites displayed significantly enhanced dielectric constants and low dielectric loss compared to the control epoxy. The nanocomposites containing 14.1 wt % BT NPs possessed dielectric constants as high as at a frequency of 10³ Hz. The dielectric loss was measured to be 0.002 at a frequency of 10³ Hz. The improved dielectric properties are accounted for the fine dispersion of the BT NPs in the epoxy thermosets. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43322.     

Carborane‐incorporated poly(silyleneethynylenephenyleneethynylene)s with different side groups

Carborane‐incorporated poly(silyleneethynylenephenyleneethynylene)s with different side groups were synthesized from corresponding poly(silyleneethynylenephenyleneethynylene)s and decaborane (B₁₀H₁₄) in the presence of acetonitrile through in‐situ reaction. The obtained polymers with o‐carborane units were characterized by using Fourier transform infrared and nuclear magnetic resonance spectroscopies, rheological measurements, differential scanning calorimetry, and thermogravimetric analysis. The results show that the properties of these carborane‐incorporated polymers vary with side groups in main chains. They possess good processability and can be crosslinked to form thermosets at temperatures less than 250°C. The thermosets exhibit excellent thermal and thermooxidative stabilities. The weight losses of the thermosets heated to 800°C in air are only 10% approximately. After pyrolysis of the thermosets in nitrogen at 1000°C, the pyrolytic products have no further weight losses up to 1000°C in air. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Novel flame retardant thermosets from nitrogen‐containing and phosphorus‐containing epoxy resins cured with dicyandiamide

A novel phosphorus‐containing epoxy resin (EPN‐D) was prepared by addition reaction of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene 10‐oxide (DOPO) and epoxy phenol‐ formaldehyde novolac resin (EPN). The reaction was monitored by epoxide equivalent weight (EEW) titration, and its structure was confirmed by FTIR and NMR spectra. Halogen‐free epoxy resins containing EPN‐D resin and a nitrogen‐containing epoxy resin (XT resin) were cured with dicyandiamide (DICY) to give new halogen‐free epoxy thermosets. Thermal properties of these thermosets were studied by differential scanning calorimeter (DSC), dynamic mechanical analysis (DMA), thermal mechanical analyzer (TMA) and thermal‐gravimetric analysis (TGA). They exhibited very high glass transition temperatures (T_gs, 139–175°C from DSC, 138–155°C from TMA and 159–193°C from DMA), high thermal stability with T_{d,5 wt %} over 300°C when the weight ratio of XT/EPN‐D is ≥1. The flame‐retardancy of these thermosets was evaluated by limiting oxygen index (LOI) and UL‐94 vertical test. The thermosets containing isocyanurate and DOPO moieties showed high LOI (32.7–43.7) and could achieve UL‐94 V‐0/V‐1 grade. Isocyanurate and DOPO moieties had an obvious synergistic effect on the improvement of the flame retardancy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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.     

Rheological behavior of chlorosulfonated polyethylene composites: Effect of filler and plasticizer

Thermosets obtained by reacting highly functionalized maleic anhydride-grafted polyethylene and a polyetherdiamine at several NH₂/MA molar ratios were characterized for their gel content, thermal, mechanical, and thermo-mechanical behavior. Gel content varied with composition and a maximum (57%) observed when NH₂/MA molar ratio was 1.5. Two melting transitions were observed for thermosets, representing the semicrystalline polyethylene fraction in the gel and sol part of the material in contrast to a single transition for the starting polyethylene. Overall crosslinking suppressed the crystallinity of the polyethylene in the thermoset. A single T_g observed in the DMA analysis suggested phase mixing between the polyethylene and polyether chains. A shift in the T_g observed was related to the degree of crosslinking in the thermosets. Tensile properties of the thermosets were observed to be a strong function of composition and the degree of crosslinking and the optimum mechanical performance was shown by thermosets when NH₂/MA molar ratio was 1.5 and 2.0. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of a novel phosphonate flame retardant and its application in epoxy resins

A novel phosphonate flame retardant additive bis(2,6‐dimethyphenyl) phenylphosphonate (BDMPP) was synthesized from phenylphosphonic dichloride and 2,6‐dimethyl phenol, and its chemical structure was characterized by Fourier transform infrared (FTIR) spectroscopy, ¹H and ³¹P nuclear magnetic resonance. The prepared BDMPP and curing agent m‐phenylenediamine were blended into epoxy resins (EP) to prepare flame retardant EP thermosets. The effect of BDMPP on fire retardancy and thermal degradation behavior of EP/BDMPP thermosets was investigated by limiting oxygen index (LOI), vertical burning test (UL‐94), cone calorimeter and thermalgravimetric analysis (TGA). The morphologies of char residues of the EP thermosets were investigated by scanning electron microscopy (SEM) and the water resistant properties of thermosets were evaluated by putting the samples into distilled water at 70°C for 168 h. The results demonstrated that the cured EP/14 wt % BDMPP composites with the phosphorus content of 1.11 wt % successfully passed UL‐94 V‐0 flammability rating and the LOI value was as high as 33.8%. The TGA results indicated that the introduction of BDMPP promoted EP matrix decomposed ahead of time compared with that of pure EP and led to a higher char yield at high temperature. The incorporation of BDMPP enhanced the mechanical properties and reduced the moisture absorption of EP thermosets. The morphological structures of char residue revealed that BDMPP benefited to the formation of a more compact and homogeneous char layer on the materials surface during burning, which prevented the heat transmission and diffusion, limit the production of combustible gases and then lead to the reduction of the heat release rate. After water resistance tests, EP/BDMPP thermosets still remained excellent flame retardancy. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42765.     

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     

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.     

Amine-cured ω-epoxy fatty acid triglycerides: Fundamental structure-property relationships

Several triacyl glycerides (2), having terminal epoxy functionalities on aliphatic residues of varying chain length, were allowed to react with either 4,4′-methylenedianiline or phthalic anhydride to give a new group of glassy network polymers with glass transition temperatures (T_gs) of 48-133 °C. Although cured 2 have substantially lower moduli than do conventional epoxy thermosets based on bisphenol A-diglycidyl ether (BADGE), the crosslinked triglycerides adhere strongly to steel and aluminum and are much more ductile and considerably tougher than commercial epoxy systems. In addition to a comparison of thermal and mechanical properties of thermosets based on 2, BADGE and common epoxidized linseed oil, reactivity differences among these epoxy resins are briefly discussed.     

Curing of epoxy systems at sub‐glass transition temperature

Three epoxy‐amine thermoset systems were cured at a low ambient temperature. Evolution of the reaction kinetics and molecular structure during cure at the sub‐glass transition temperature was followed by DSC and chemorheology experiments. The effect of vitrification and the reaction exotherm on curing and final mechanical properties of the epoxy thermosets was determined. Thermomechanical properties of the low‐temperature cured systems depend on the reaction kinetics and volume of the reaction mixture. Curing of the fast‐reacting system in a large volume (12‐mm thick layer) resulted in the material with T_g exceeding the cure temperature by 70–80°C because of an exothermal temperature rise. However, the reaction in a too large volume (50‐mm layer) led to thermal degradation of the network. In contrast, thin layers (1.5 mm) were severely undercured. Well‐cured epoxy thermosets could be prepared at sub‐T_g temperatures by optimizing reaction conditions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3669–3676, 2006     

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.