Cyanate Ester Resin with High Heat‐Resistance and Degradable Diacetal Structure: Synthesis, Polymerization, and Properties

Liu, Linze; Xia, Yuhan; Wang, Lian; Shi, Rui; Yan, Shuai; Zhao, Xingyu; Jin, Yongzhong; Sheng, Yuping

doi:10.1002/mame.202200423

Cited by 6 publications

(4 citation statements)

References 56 publications

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“…We also compare how H bonding of THF with water and with sorbitan esters affects the COC band of THF. With pure THF, we observe a dominant COC stretch peak at ≈1,070 cm −1 (Liu et al, 2022), and a significantly smaller peak at 1,027 cm −1 (Sionkowska and Płanecka, 2013) (Figure 1). As mentioned above, upon mixing with water, the peak at ≈1,070 cm −1 splits into three peaks, at ≈1,070 cm −1 , ≈1,050 cm −1 and ≈1,040 cm −1 .…”

Section: Tailmentioning

confidence: 88%

Effect of sorbitan ester structure on the separation between tetrahydrofuran and water

Bartokova,

Marangoni,

Laredo

et al. 2023

Front. Soft Matter

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This study separates tetrahydrofuran (THF)-water mixtures containing varying THF percentages, using sorbitan esters (Spans) with different tail characteristics. We probe the separation mechanisms using attenuated total reflectance-Fourier transform infrared spectroscopy and small angle X ray scattering (SAXS). THF and water are miscible and interact through hydrogen bonds. Water splits the COC absorbance band of THF into a peak at ≈1,070 cm−1 (crystalline THF) and a dominant peak at ≈1,050 cm−1 (glassy THF), indicating disorder. Depending on the Span, separation occurs for mixtures containing up to 70% THF (v/v, relative to water). Spans with unsaturated tails separate the lowest THF percentages. Tail length and number of Span tails enhances ordering of THF, and the crystalline THF peak at ≈1,070 cm−1 dominates. Spans interact with THF through hydrogen bonds, as reflected in the splitting of the COC band of THF. Furthermore, C-H…O hydrogen bonds cause a blueshift in the νas(CH2) band of Spans with increasing THF. This effect is most significant in Span 40 and 60, indicating that they interact with THF more strongly than Span 20, Span 80 and Span 85. In contrast, they interact with water less strongly than Span 20, Span 80 and Span 85, as indicated by their flocculation at low THF percentages. Therefore, we propose that separation between THF and water occurs primarily through two mechanisms: 1) Span 20, Span 80 and Span 85 compete against THF for interactions with water through their hydrophilic head, and 2) Span 40 and Span 60 preferentially interact with THF through their tails. Nonetheless, water also interacts with the heads of Span 40 and Span 60, as indicated by SAXS. SAXS shows that in THF Spans self-assemble into micelles, which aggregate into either surface fractals or mass fractals. There are two persistence lengths because of the limited order in THF. Water orders self-assembled structures, likely by favoring the formation of micelles which host water in their interior. Therefore, we identify a single persistence length (≈25 Å), representative of the distance between the micelle centers.

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Section: Tailmentioning

confidence: 88%

Effect of sorbitan ester structure on the separation between tetrahydrofuran and water

Bartokova,

Marangoni,

Laredo

et al. 2023

Front. Soft Matter

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“…19,20,46 Moreover, Xia et al synthesized a novel degradable cyanate ester featuring a diacetal structure with a high T g of 294 °C. 17 In our previous work, Wang et al prepared two high heat-resistant and degradable polybenzoxazines with T g of around 300 °C due to the presence of the rigid diacetal structure. 47 These studies demonstrate the potential of the acetal structure in achieving both high thermal resistance and degradability in polymers.…”

Section: ■ Introductionmentioning

confidence: 99%

“…With the increasing application of polymer materials, the environmental impact of their waste has also been growing, particularly for thermosetting polymers with high cross-linking density. Three-dimensional cross-linking structures provide excellent heat resistance, rigidity, and dimensional stability. − However, they also present significant challenges in terms of degradation and recovery. − Many researchers have attempted to make thermosetting resins degradable by incorporating unstable structures such as ester, acetal, sulfur bond, Schiff base, and others. ,− It is important to acknowledge that these unstable structures can also have some adverse effects on the performance of materials, especially in terms of heat resistance. − It has been observed that a high cross-linking density leads to improved thermal stability of the cross-linking structure and enhanced heat resistance of the material. However, achieving degradability in materials often requires a relatively low cross-linking density and the inclusion of unstable cross-linking structures.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, researchers have shown increasing interest in rigid acetal structures due to their degradability and excellent heat resistance. For instance, Ma et al successfully incorporated an acetal structure into epoxy resin and polyurethane, resulting in materials that exhibited both degradability and good heat resistance. ,, Moreover, Xia et al synthesized a novel degradable cyanate ester featuring a diacetal structure with a high T g of 294 °C . In our previous work, Wang et al prepared two high heat-resistant and degradable polybenzoxazines with T g of around 300 °C due to the presence of the rigid diacetal structure .…”

Section: Introductionmentioning

confidence: 99%

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Preparation and Properties of a Phosphorus-Free Intrinsic Flame-Retardant and High Thermal Resistant Polybenzoxazine with Good Degradability

Jiang,

Chen,

et al. 2024

ACS Appl. Polym. Mater.

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Polybenzoxazines are a type of thermosetting resin with good thermal resistance. A flame-retardant and degradable polybenzoxazine (ERY-a) was synthesized by a special bisphenol containing a bridging diacetal structure (ERY) and aniline. A systematic comparative study was conducted between ERY-a and bisphenol A/aniline-type benzoxazine (BA-a). Their chemical structures were confirmed by Fourier transform infrared (FTIR) spectra and nuclear magnetic resonance (NMR) spectra. The curing behaviors and polymerization reactions were analyzed by differential scanning calorimetry (DSC) and FTIR spectra. Dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA) were used to investigate their thermal properties, and the results showed that the cured ERY-a, referred to as P(ERY-a), exhibited a notable glass transition temperature T g of 297 °C and a char yield of 51% under N 2 at 800 °C, both of which were significantly higher than those of cured BA-a. Furthermore, the flame retardancy of P(ERY-a) and ERY-a-based composites was assessed through microcalorimetry (MCC) and vertical combustion testing. The findings highlighted that the superior flame retardancy and low heat release capacity (HRC) of P(ERY-a) were due to the presence of the diacetal structure. More importantly, the cross-linked P(ERY-a) can be degraded in a solvent via the cleavage of the diacetal structure, and optimal degradation conditions were systematically studied. Moreover, the carbon fiber from the ERY-a-based composite can be easily recycled through the degradation of ERY-a.

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3D printing of cyanate ester resins with interpenetration networks for enhanced thermal and mechanical properties

Zaman,

Favela,

Herrera

et al. 2024

J of Applied Polymer Sci

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Cyanate ester (PT‐30) resin possesses exceptional thermal and mechanical properties, including high heat distortion temperature, high glass transition temperature (Tg), and outstanding mechanical characteristics. Conversely, the Tg of the homopolymer of tris(2‐hydroxyethyl)isocyanurate triacrylate (T‐acrylate) surpasses that of other acrylates. The combination of PT‐30 and T‐acrylate results in the formation of an interpenetrating polymer network (IPN) through a dual curing mechanism. Furthermore, the combination of these two polymers enables the tuning of rheology for shear thinning behavior for Ink Extrusion 3D printing technology by adjusting the amount of photoinitiator and rheological modifier. Here, 3D printable ink was formulated using PT‐30, T‐acrylate with a higher Tg, a photoinitiator, and a powdered rheological additive. The printed structures underwent a dual‐curing process involving exposure to UV light and thermal curing. Thermomechanical properties of the printed samples were characterized using dynamic mechanical analysis, thermogravimetric analysis, and tensile testing. The successful formation of an IPN structure through the polymerization of T‐acrylate and PT‐30 was observed, resulting in improved mechanical properties and an elevated Tg. The Fourier transform infrared spectroscopy analysis verified the formation of cross‐linked samples. Overall, this study demonstrates the feasibility of Ink Extrusion 3D printing, using a cyanate ester resin and tris(2‐hydroxyethyl)isocyanurate triacrylate with a dual‐curing mechanism. The enhanced mechanical properties at elevated temperatures (~80% retention of room temperature tensile strength at 200°C for sample with 70/30 wt%) and high Tg of 349 ± 3°C for printed structures shown in this study make them suitable for high‐performance structural applications in industries such as aerospace, defense, and microelectronics.

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Cyanate Ester Resin with High Heat‐Resistance and Degradable Diacetal Structure: Synthesis, Polymerization, and Properties

Cited by 6 publications

References 56 publications

Effect of sorbitan ester structure on the separation between tetrahydrofuran and water

Effect of sorbitan ester structure on the separation between tetrahydrofuran and water

Preparation and Properties of a Phosphorus-Free Intrinsic Flame-Retardant and High Thermal Resistant Polybenzoxazine with Good Degradability

3D printing of cyanate ester resins with interpenetration networks for enhanced thermal and mechanical properties

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