The impact of ultra-low amounts of introduced reactive POSS nanoparticles on structure, dynamics and properties of densely cross-linked cyanate ester resins

Bershteĭn, V. A.; Fainleib, Alexander; Egorova, L. M.; Grigoryeva, Olga; Kirilenko, D. A.; Konnikov, Semen; Ryzhov, V. A.; Starostenko, Olga; Yakushev, P. N.; Yagovkina, M. A.; Saiter, Jean‐Marc

doi:10.1016/j.eurpolymj.2015.03.022

Cited by 30 publications

(55 citation statements)

References 41 publications

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“…1) have been confirmed in the CER/ECH-POSS mixtures using FTIR spectroscopy technique. [29,32] One can suppose that CER molecules will react with epoxy groups of ECH-POSS on a surface of nanoparticles with formation of oxazolidinone containing linear fragments, whereas the remote from surface CER molecules will rather react to each other with formation of cyanurate cycles. The final hybrid material consists of the organic network with cyanurate junctions and embedded single inorganic ECH-POSS nanoparticles as additional inorganic junctions connected by oxazolidinone containing bridges (Fig.…”

Section: Resultsmentioning

confidence: 99%

“…Similar effects were registered in the far-IR spectra of these nanocomposites with other ultra-low ECH-POSS contents, 0.025 or 0.5 wt %. [32] One can see the substantial reduction of the intensity of the 76 cm À1 band indicating some suppression of vibrational dynamics of rings. Additionally, some disturbance in the system of torsional skeletal vibrations is also observed: the maximum at 230 cm À1 displaced to 220 cm À1 .…”

Section: Network Vibrational Dynamics (Far-infrared Spectra)mentioning

confidence: 96%

“…Typically, the positive effect of POSS addition on CER network properties was observed at POSS content not more than 1-5%. Recently, [29,32] authors revealed the anomalously large positive influence of the introduction of ultra-low amounts (e.g. 0.025 wt%) of epoxycyclohexyl-functionalized POSS (ECH-POSS) nanoparticles on dynamics and thermal and mechanical properties of the CER matrix.…”

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confidence: 99%

“…hybridization of components in these composites, occurred that has earlier been evidenced by appearing the absorption band at 1738 cm À1 in the nanocomposite spectra, which confirmed the presence of oxazolidinone rings formed due to this co-reaction. [29,32] To characterize the changes in molecular dynamics in the matrix, caused by covalent incorporation of ECH-POSS nanoparticles into CER network, far-IR spectra of neat cured CER matrices and the nanocomposites were registered at 20°C over the range from 20 to 300 cm À1 using FIS-21 Hitachi spectrometer (Japan) with a resolution of 1 cm À1 . The film samples thickness equaled about 100 μm.…”

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confidence: 99%

“…However, to our knowledge the specific papers on comparison of properties of various CER are not published. Because of the discrepancy between the analytical techniques and, for the same technique, between the sample preparations, comparison between two values of, for example, T g or T d or mechanical strength from distinct publications is tricky, if not impossible.The nanocomposites of PCN with montmorillonite, [8][9][10][11][12][13] carbon nanotubes, [14,15] nanostructured aluminum borate, [16] ZnO, [17] ZrW 2 O 8 , [18] nanosilica, [19] and polyhedral oligomeric silsesquioxanes (POSS) [20][21][22][23][24][25][26][27][28][29][30][31][32] have been developed and characterized. In the majority of these works, the authors have studied usually only one type of CER as well.…”

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Thermostable cyanate ester resins and POSS-containing nanocomposites: influence of matrix chemical structure on their properties

Bershteĭn

Fainleib

Yakushev

et al. 2015

Polym. Adv. Technol.

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Thermostable densely crosslinked cyanate ester resins (CER) with different chemical structures, derived from monomer dicyanate esters of bisphenol E (DCBE), bisphenol A (DCBA), hexafluorobisphenol A (6F-DCBA) or from cyanated phenol-formaldehyde oligomer PT-30, and the nanocomposites based thereon, with 0.01 to 10 wt% epoxycyclohexyl-functionalized polyhedral oligomeric silsesquioxane (ECH-POSS), were synthesized and characterized by means of dynamic mechanical analysis, differential scanning calorimetry, far-infrared, and creep rate spectroscopy techniques. As shown, thermal and mechanical properties increased in a row of matrices prepared from DCBE < DCBA < 6F-DCBA < PT-30. Thus, these matrices with T g = 248, 275, 300, and~400°C (DMA, 1 Hz), respectively, had dynamic modulus E′ values of 1.8, 2.7-3.0, and 3.6 GPa at 20°C; high rigidity (dynamic modulus of about 1-2 GPa) retained at temperatures up to 200°C for DCBE matrix, 250°C for DCBA and 6F-DCBA matrices, but up to 380°C for PT-30-based matrix. The maximal effects from introducing ECH-POSS nanoparticles, covalently embedded into CER network, were attained mainly at their ultra-low contents (<<1 wt%); however, the ECH-POSS impact decreases in a row of matrices prepared from DCBE > DCBA > 6F-DCBA > PT-30. Copyright © 2015 John Wiley & Sons, Ltd.Keywords: cyanate ester resins; nanocomposites; synthesis; chemical structure; properties INTRODUCTIONCyanate ester resins (CER) are an important class of high performance materials. Polycyclotrimerization of cyanate esters leads to formation of high-temperature thermosetting polymers, polycyanurates (PCN), of a high crosslink density with triazine cycles in network junctions. [1][2][3][4][5][6] They have received much attention because of their unique combination of properties including stability at temperatures up to 350-420°C, high glass transition temperature (≥250°C), high fire, radiation, and chemical resistance, low water absorption and low outgassing, high adhesion to different substrates, and excellent dielectric properties (ε ≈ 2.6-3.1).[2-5] As a result, CER are widely used as the structural or functional materials in aeronautics, space (composite strakes, fins, nose radomes, and heat shields), printed circuit boards, and as encapsulants, adhesives, etc.[7] Several commercial CER of different chemical structures are known.[3] As a result of polycyclotrimerization reaction, CER monomer transforms into polycyanurate network (Fig. 1). In case of high purity of the monomer, the polymer network with a regular 3D structure is formed, and the only difference of the chemical structure of the materials obtained from different CER is fragment R between the cyanurate junctions in the networks (Fig. 1). An influence of R fragment in polycyanurates on structure-properties relationships, changes in FTIR spectra, glass transition temperatures, T g , thermal or thermal oxidative degradation, T d , adhesion, and some mechanical properties can be understood from some reviews and books, [2][3][4] where the data on polycyanura...

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Section: Resultsmentioning

confidence: 99%

Section: Network Vibrational Dynamics (Far-infrared Spectra)mentioning

confidence: 96%

mentioning

confidence: 99%

mentioning

confidence: 99%

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confidence: 99%

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Thermostable cyanate ester resins and POSS-containing nanocomposites: influence of matrix chemical structure on their properties

Bershteĭn

Fainleib

Yakushev

et al. 2015

Polym. Adv. Technol.

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High heat‐resistant (250°C) epoxy resin composites with excellent dielectric properties

Wang

Feng

Zhang

et al. 2022

J of Applied Polymer Sci

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Insulated gate bipolar transistor (IGBT) is the core of electric energy conversion and circuit control, which is widely used in the field of electric vehicles. Higher service temperature, higher power density, and higher operating voltage are the tendency for IGBT in which packing materials have to possess more stable temperature resistance and better insulating properties. In this work, cyanate ester (CE) and polyhedral oligomeric silsesquioxanes (POSS) are introduced into epoxy with various filling ratio to improve the dielectric and thermal properties. The curing process of every system is determined by non‐isothermal differential scanning calorimetry (DSC). N and Si element distribution mappings indicate that there are good compatibility between POSS, CE, and epoxy. The dielectric test shows that the dielectric constant decreases from 4.34 to 2.84 at 1 MHz and from 4.76 to 2.93 at 1 kHz when the filling ratio is 60 wt%. Meanwhile, the DC breakdown strength increases from 172.7 to 286.4 kV/mm. Furthermore, the glass transition temperature (Tg) increases from 180 to 263°C and the yield of residual carbon increases from 6.2% to 23.7%. A new packing material, which can endure 250°C of operating temperature and has excellent dielectric properties has been synthesized.

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High performance multi‐functional cyanate ester oligomer‐based network and epoxy‐POSS containing nanocomposites: Structure, dynamics, and properties

et al. 2020

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The aim of this research was the detailed analysis and estimation of CER oligomer‐based nanocomposites for applications under extreme high temperature conditions. Thermostable nanocomposites based on cross‐linked cyanate ester resin (CER), derived from PRIMASET PT‐30 multi‐functional oligomer and doped by 0.025wt% to 10wt% epoxycyclohexyl‐functionalized polyhedral oligomeric silsesquioxane (ECH‐POSS) nanoparticles, were synthesized and characterized using TEM, mid‐, and far‐IR spectroscopy, and by DMA, DSC, CRS, and TGA techniques. At nanoparticles contents less than 1wt%, basically their molecular level dispersion in the matrix is suggested, whereas their clusters of about 20 to 30 nm in diameter were observed at 2wt% and 10wt% ECH‐POSS. In correlation with the results of structural analysis, the ambivalent influence of the nanoparticles, depending on their content, on the dynamics and properties of nanocomposites was revealed. The “constrained dynamics” effects caused by post‐curing and covalent embedding ECH‐POSS units into the matrix were registered by DMA, far‐IR spectroscopy and CRS. Highly cooperative glass transition with Tg ≈ 400°C (DMA, 1 Hz) was observed, and at the limit total suppression of glass transition could be achieved. The obvious superiority of the studied nanocomposites over the CER nanocomposites synthesized from monomeric dicyanate ester of bisphenols, especially at high temperatures, was shown.

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The impact of ultra-low amounts of introduced reactive POSS nanoparticles on structure, dynamics and properties of densely cross-linked cyanate ester resins

Cited by 30 publications

References 41 publications

Thermostable cyanate ester resins and POSS-containing nanocomposites: influence of matrix chemical structure on their properties

Thermostable cyanate ester resins and POSS-containing nanocomposites: influence of matrix chemical structure on their properties

High heat‐resistant (250°C) epoxy resin composites with excellent dielectric properties

High performance multi‐functional cyanate ester oligomer‐based network and epoxy‐POSS containing nanocomposites: Structure, dynamics, and properties

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