Heat-resistant polymers - current status

The current state of the art is reviewed in respect of heat-resistant polymers, which are used as elastomers, and as thermoplastic or thermosetting compositions.     

Preparation of thermoset composites from natural fibres and acrylate modified soybean oil resins

Structural composites with a high content of renewable material were produced from natural fibres and an acrylated epoxidized soybean oil resin. Composites were prepared by spray impregnation followed by compression moulding at elevated temperature. The resulting composites had good mechanical properties in terms of tensile strength and flexural strength. Tensile testing as well as dynamical mechanical thermal analysis showed that increasing the fibre content, increased the mechanical properties. The resin can be reinforced with up to 70 wt % fibre without sacrifice in processability. The tensile modulus ranged between 5.8 and 9.7 GPa depending on the type of fibre mat. The study of the adhesion by low vacuum scanning electron microscopy shows that the fibres are well impregnated in the matrix. The aging properties were finally evaluated. This study shows that composites with a very high content of renewable constituents can be produced from soy bean oil resins and natural fibres. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Melt spinning and metal chloride vapor curing process on polymethylsilsesquioxane as Si?O?C fiber precursor

Melt spinning process of polymethylsilsesquioxane (PMSQ) at 403–453 K was investigated as a Si? O? C fiber precursor in terms of averages and distributions of spun fiber diameters. Because of fusible character of PMSQ at low temperature, the spun fibers were exposed to vapors of various metal chlorides (SiCl₄, Si(CH₃)Cl₃, TiCl₄, and BCl₃) to promote the fiber curing. Cured fibers were investigated by FTIR and TG analyses. In a case of the fiber synthesized with SiCl₄ curing, tensile tests on the pyrolyzed fibers were performed. Exposure of the synthesized fiber at high temperature with a flame of an oxygen‐gas burner was examined. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Preparation of binary and hybrid epoxy nanocomposites containing graphene oxide and rubber nanoparticles: Fracture toughness and mechanical properties

Binary and hybrid epoxy nanocomposites modified with graphene oxide (GO) and core–shell rubbers (CSR) were synthesized via the solvent-exchange method. X-ray diffraction analysis and scanning electron microscopy of the samples showed a homogeneous dispersion of GO and CSR in the epoxy matrix. The tensile modulus and tensile strength of the samples modified with CSR decreased continuously with increasing CSR content; however, with the addition of only 0.05 phr GO to the neat epoxy and rubber-modified epoxy, these properties significantly increased. The use of GO and CSR individually improved the fracture toughness, but the impact of GO was greater. The simultaneous use of GO and CSR improved both the fracture toughness and the mechanical properties. Our investigation of the toughening mechanism indicated that crack deflection–bifurcation, crack pinning, and particle debonding–pullout in the presence of GO nanosheets and limited rubber particle cavitation contributed to fracture toughness improvement in the hybrid systems. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46988.     

Phosphorus–nitrogen-type fire-retardant vinyl ester resin with good comprehensive properties

In this study, a series of fire-retardant vinyl ester resins (VERs) were obtained via the copolymerization of phosphorus–nitrogen-containing acrylate [1,3,5-triglycidyl isocyanurate (TGIC)–acrylic acid (AA)–9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)] and the widely used vinyl ester resin 901 (901-VER). The influences of the TGIC–AA–DOPO additive amount on 901-VER were comprehensively evaluated via the measurement of the flame retardancy, thermal performance, and mechanical properties. In the case of 30 and 40% TGIC–AA–DOPO, the thermosets acquired limited oxygen index values of 30.8 and 31.7%, respectively, and reached vertical burning (UL-94) ratings of V-1 and V-0, respectively. In addition, their peak heat-release rates, average heat-release rates, total heat release values, average effective heats of combustion, and total smoke productions decreased significantly. These results demonstrated the great progress of 901-VER in fireproofing performance. More importantly, the flame-retardant VER thermosets showed good thermal properties and castings, and glass-fiber-reinforced composites based on the developed fire-retardant VERs possessed comparable tensile strength, flexural strength, and better tensile modulus comparing to those based on neat 901-VER when the TGIC–AA–DOPO amount was no greater than 30%. From an integrated perspective, 901-VER with 30% TGIC–AA–DOPO was the best desired. The excellent flame retardancy, thermal performance, and mechanical properties promise the as-obtained VER important applicable values. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47997.     

Synthesis of Schiff base–containing benzoxazine derivatives

The excellent chemical and physical properties of benzoxazine resins and the functionality of Schiff bases were combined in one compound's structure, creating newly designed benzoxazine derivatives that can form complexes with metals. The new type of benzoxazine monomer was synthesized via the ring-closure reaction of formaldehyde, aniline, and three newly designed Schiff bases. The presence of the Schiff base in the molecular structure of these novel benzoxazine monomers enables them to trap metals as the functional compounds, like Cu, from a solution. Thermally initiated polymerization occurs at a lower temperature by the formation of intermolecular and intramolecular hydrogen bonds between imine, oxazine, Schiff base hydroxyl groups, and the newly generated hydroxyl groups. The thermal behavior of the bisbenzoxazine monomers was investigated with Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and differential scanning calorimetry, and then they were cured at 120, 180, and 230°C. According to the magnetic susceptibility, FTIR, scanning electron microscopy with energy dispersive X-ray spectroscopy, TGA, and microwave plasma atomic emission spectroscopy results, it is shown that Cu(II) complexes of the compounds were also succesfully synthesized, and they proved to be successful in catching metal. This is due to the functionality of Schiff bases forming the metal complexation in the compounds. The poly(bisbenzoxazine)s also showed high limiting oxygen index (31–37), low ring-opening temperature (150–190°C), high char yield (35%–49%), and excellent thermal stability, due to the highly crosslinked nature of the polymers. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47908.     

Materials containing benzocyclobutene units with low dielectric constant and good thermostability prepared from star-shaped molecules

With the development of ultralarge-scale integrated circuits, polymers with low dielectric constant and high thermal stability have aroused great interest. We prepared two novel bridged siloxane-based benzocyclobutene (BCB) star-shaped monomers, tetrakis[dimethyl siloxy-4-(1′,1′-dimethyl-1′-ethyl silicon)-benzocyclobutene] (TDSDES-BCB) and tetrakis(hexamethyl siloxane vinyl-benzocyclobutene) (THSV-BCB), and the corresponding resins were obtained by curing. The structures of TDSDES-BCB and THSV-BCB were confirmed by ¹H-NMR, ¹³C-NMR, and ²⁹Si-NMR spectra and time-of-flight mass spectrometry analysis. The curing behavior of these monomers was investigated by Fourier transform infrared spectroscopy and differential scanning calorimetry. The dielectric constant of cured TDSDES-BCB is only 2.43 at 10 MHz (that of THSV-BCB is 2.46). In addition, these resins display high thermal stability: the 5 wt % weight loss temperature of cured TDSDES-BCB is about 467 °C (454 °C for THSV-BCB resin). The excellent low dielectric property is attributable to the free volume created by the star-shaped structure and crosslinked network structure of BCB after curing. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47458.     

Thermal and dynamic mechanical behavior of epoxy composites reinforced with post-consumed yerba mate

Yerba mate (YM) is widely consumed in Latin American countries, and its residues can be used as bio-resources such as reinforced in epoxy composites. The present work aims to produce epoxy resin composites and evaluate the influence of post-consumed YM as reinforcement. The concentrations of YM used were 5, 10, and 20% (wt/wt). Chemical, thermal, morphological, and dynamic mechanical behaviors were explored. The YM incorporation did not influence chemically on the epoxy structure and a pull-out phenomenon was observed as YM content increased. The YM at lower concentrations (5 and 10%) led to higher values of activation energies calculated from model-free isoconversional methods. On the other hand, the composite e/YM 20 wt% improved all dynamic-mechanical properties. YM proved to be a suitable and cheap reinforcement for epoxy resin.     

High biorenewable content acrylate photocurable resins for DLP 3D printing

Green chemistry and green engineering concepts have been combined to develop novel sustainable polymeric materials. Solvent free photocurable acrylate resins with biorenewable carbon content of 75%–82% suitable for application in DLP 3D printing technology were composed by commercially available bio-based materials, acrylated epoxidized soybean oil (AESO), isobornyl methacrylate (IBOMA), methacrylic ester (ME), tetrahydrofurfuryl acrylate (THFA), and tetrahydrofurfuryl methacrylate (THFMA). They demonstrated high printing accuracy and good adhesion between layers. The monitoring of photocross-linking kinetics of high biorenewable content acrylate photoresins by the real-time photorheometry and analysis of their rheological parameters was carried out. Synthesized polymers exhibited high yield of insoluble fraction and thermal decomposition temperature at the weight loss of 10% above 300°C. Polymers AESO/IBOMA and AESO/THFMA showed the highest values of tensile modulus and tensile strength. Biodegradability of the synthesized polymers AESO/ME, AESO/THFA, and AESO/THFMA was investigated by measuring oxygen consumption in a closed respirometer. Such AESO-based polymers can be a competitive solution to replace petroleum-derived polymeric materials in additive manufacturing and reduce the environmental impact.