HIGH PERFORMANCE POLYMERS
·
2026
·
IF 1.8
Zhaolong Yin,Yongcheng Zhang,Cheng Tang,Can Huang,Yilin Lizhuo,Rui Chen,Zhaorui Wang,Min Liu,Quan Zhou
Phthalonitrile (PN) resins exhibit outstanding thermal and mechanical properties but suffer from intrinsically high melting temperatures and sluggish curing kinetics, which severely restrict their processability and manufacturability. In this work, a eutectic blending strategy based on ternary PN monomers was employed to markedly depress the melting temperature, enabling mild and controllable melt prepolymerization with a diamine curing agent. This approach produced a low-melting phthalonitrile prepolymer (MPPh) exhibiting a viscosity below 1 Pa·s at 88°C, providing a stable melt-processing window. DSC and FTIR analyses revealed that the prepolymerization predominantly proceeded through linear chain growth via amino-nitrile addition reactions. To address the inherently low curing reactivity of MPPh, 3-aminophenylacetylene (APA) was introduced as a reactive diluent to activate the curing process and further tailor the rheological behavior. The modified resin (MP-m) demonstrated significantly enhanced curing efficiency and a reduced viscosity below 1 Pa·s at 66°C, excellent isothermal stability, and pronounced shear-thinning behavior. The cured MP-m resin retained excellent thermal stability and mechanical performance. These findings provide a simple and solvent-free strategy for the preparation of low-melting-point phthalonitrile, broadening the practical application potential of PN resins in high-temperature composite manufacturing.
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DOI
高影响因子
Polymer Chemistry
·
2024
·Vol. 15
·期 21
·2157-2166
·
IF 4.1
Muyao Gao,Qian Wu,Tianhao Li,Li Liu,Bing Li,Yujie Song,Ming Liu
The superior high-temperature resistance of phthalonitrile resins shows great application potential in extreme environments. However, the high rigidity and strong intermolecular force lead to a high melting point and harsh processing conditions. To improve the processability of phthalonitrile resins, Si–O–Si chain segments with long bond lengths and large bond angles were introduced, and a liquid phthalonitrile monomer was successfully prepared. The flexible segment effectively improved the processing performance of the monomer, which was characterized by a low melting point (−10.8 °C), low viscosity (∼4.3 Pa s at 30 °C), and good solubility in common solvents. The cured resin showed excellent thermal properties, credited to the high bond energy from Si–O bonds and the aromatic heterocyclic structures formed during curing. Moreover, the resin also demonstrated good flame retardancy without flame retardant additives, and low heat release capacity (32.7 J g−1 K−1), and passed the V-0 rate of the UL 94 test. This high-performance resin, integrating easy processing, high-temperature resistance, and flame retardancy, makes phthalonitrile a suitable resin to serve in harsh environments.
研究领域:
材料科学
·
高分子化学
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DOI
高影响因子
APPLIED THERMAL ENGINEERING
·
2017
·
IF 3.444
Mehdi Derradji,Xuemei Song,Abdul Qadeer Dayo,Jun Wang,Wen-bin Liu
Highly filled phthalonitrile nanocomposites, reinforced with both native and silane surface modified nano-BN were investigated for their mechanical and thermal properties. The nanocomposites were prepared by a solution blending technique followed by compression molding. The thermal conductivity was investigated as the core of the study along with a bending test, a morphological behavior, thermal stability investigations, and thermomechanical properties measurements. The highest thermal conductivity value of 4.69 W/m K was obtained at the maximum nanofillers loading of 30 wt.% treated BN . A high resolution TEM confirmed that the exceptional enhancements in the thermal conductivity are related to the formation of an effective conductive path assured by the silane surface modified nano-BN. The bending test also revealed consequent improvements in both the strength and modulus as the amount of the nanofillers increased. The SEM investigations revealed positive changes in the surface morphology of the neat resin, with a rougher and homogeneous state of surfaces for the hybrids. Moreover, the thermal stability at the maximum fillers loading was found to be one of the best ever reported in the field of high performance polymer-based composites, with a 5 wt.% weight loss temperature of 551 °C.
研究领域:
材料科学
·
聚合物复合材料
·
热管理
·
纳米材料
·
应用物理
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DOI
高影响因子
REACTIVE & FUNCTIONAL POLYMERS
·
2018
·
IF 2.975
An-ran Wang,Abdul Qadeer Dayo,Li-wu Zu,Yi-le Xu,Dan Lv,Sha Song,Tao Tang,Wen-bin Liu,Jun Wang,Bao-chang Gao
Two bio-based phthalonitrile (PN) monomers , eugenol-based phthalonitrile (EPN) and guaiacol-based phthalonitrile (GPN), were successfully synthesized by the reaction of 4-nitrophthalonitrile with eugenol and guaiacol derived from clove and lignin, respectively, in the presence of potassium carbonate via nucleophilic substitution reaction . Their chemical structures were confirmed by the Fourier transform infrared spectra (FTIR), hydrogen and carbon nuclear magnetic resonances ( 1 H and 13 C NMR), and elemental analysis . The curing behavior of the blends of the prepared PN monomers with 10 wt% of 4-(4-aminophenoxy)-phthalonitrile (4-APN) as curing agent was evaluated by FTIR and differential scanning calorimetry (DSC), while rheometer was used to analyze the processability of the blends. Moreover, the thermomechanical and thermal properties of the polymers were studied by dynamic mechanical analyzer (DMA) and thermogravimetric analysis (TGA). The results confirmed that the bio-based PN monomers and its blends show low melting temperatures, wide processing windows (>186 °C), and low melt viscosity (<0.03 Pa·s). The cured bio-based PN resins exhibited higher glass transition temperature and better thermal stability and toughness than those of typical bisphenol A-based phthalonitrile polymer. Meanwhile, the phthalodinitrile resins form a homogeneous, void-free network structure, which also confirm the excellent thermal and mechanical properties of the polymers.
研究领域:
材料科学
·
有机化学
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DOI
高影响因子
JOURNAL OF APPLIED POLYMER SCIENCE
·
2018
·Vol. 135
·期 31
·46578
·
IF 1.901
Dan Lv,Abdul Qadeer Dayo,An-Ran Wang,Sadia Kiran,Yi-Le Xu,Sha Song,Wen-bin Liu,Jun Wang,Bao-Chang Gao
A new high-performance copolymer was successfully obtained via concerted catalysis polymerization of mono-functional benzoxazine (P-a) and self-promoted 4-aminophenoxy phthalonitrile (4-APN) monomers. The FTIR and DSC curves of the P-a/4-APN in different blend ratios suggested that the monomer blends can be completely cured without the addition of curing additive. The P-a/4-APN copolymers were cured at relatively lower curing temperatures and time. The TGA curves revealed that the P-a/4-APN copolymers have good thermal stability in terms of T 5 , T 10 , and char yield. A gradual increase in the glass transition temperature ( T g ) values and decline were seen in the storage modulus as the loading of 4-APN was increased from 10 to 30 wt % in the copolymer. The SEM analyses showed that copolymer's fracture surface is dendritic, showing the stress has been dispersed to a certain extent. The study revealed that the poly(P-a/4-APN) copolymer have much better thermal stabilities than the poly(P-a), and the prepared copolymer can be used as a high-performance thermosetting resin. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135 , 46578.
研究领域:
材料科学
·
高分子化学
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DOI
高影响因子
POLYMER COMPOSITES
·
2019
·Vol. 41
·期 1
·134-141
·
IF 2.268
Mehdi Derradji,Abdeldjalil Zegaoui,Aboubakr Medjahed,Wenbin Liu,Abdelkhalek Henniche
Phthalonitrile resins as one of the leading high performance polymers are currently used in highly exigent applications. Herein, aiming to achieve the best combination of mechanical, thermal, and nuclear shielding performances, we prepared hybrid materials based on the typical phthalonitrile resin and the silane surface modified chopped carbon fibers and tungsten carbide nanoparticles. The obtained results suggested that a synergistic combination between the three constituent was clearly achieved leading to excellent mechanical and gamma rays shielding properties. For instance, the tensile and bending strengths reached up to 505 and 584 MPa for the composite containing 20 and 30 wt% of carbon fibers and tungsten carbide nanoparticles, respectively. Similarly, the gamma rays screening ratio also reached the exceptional value of 39% for the same 2 cm thick hybrid. Finally, the as such described hybrid materials proved that a multi-approach strategy is often the best solution to achieve the requirements of highly exigent applications.
研究领域:
材料科学
·
高分子化学
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DOI
高影响因子
CHINESE JOURNAL OF POLYMER SCIENCE
·
2019
·Vol. 38
·期 1
·72-83
·
IF 2.804
Han Yue,Tang Dong-Hao,Wang Guang-Xing,Sun Ya-Nan,Guo Ying,Zhou Heng,Qiu Wen-Feng,Zhao Tong
Vanillin was used as sustainable source for phthalonitrile monomer synthesis, and allyl/propargyl ether moieties were introduced to improve the processability at the minimal cost of thermal properties. The synthesis route was optimized to minimize side-reactions and simplify post-processing, and the monomers were obtained in high purity and good yields. The curing behavior, mechanism, and processability of the monomers were studied, and the thermal properties of cured polymers were evaluated. Of the two monomers, the allyl ether-containing one exhibited a wide processing window of 185 °C, and was mainly cured into phthalocyanine and linear aliphatic structures through self-catalytic curing process. Also, the glass transition temperature was higher than 500 °C. In contrast, the propargyl ether-containing monomer could only be partially cured, and heat resistance was found to be compromised. Compared with traditional petroleum-based phthalonitrile resins, the bio-based monomers could be cured without the addition of catalysts, and improvement in processability was achieved at no cost of thermal performances.
研究领域:
材料科学
·
高分子化学
·
可持续材料
·
有机化学
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产品关联
DOI
高影响因子
POLYMER
·
2019
·
IF 3.771
Yuan Zu,Lishuai Zong,Jinyan Wang,Xigao Jian
The development of high-temperature resistant polymers and their composites is of particular interest because of their ever-growing applications. Herein, a family of branched phthalonitrile resins based on different bisphenols (Hydroquinone, 4,4′-Biphenol, m -Dihydroxybenzene, 1,6-Dihydroxynaphthalene, 2,6-Dihydroxynaphthalene) and phenyl- s -triazine, endcapping with 4-nitrophthalonitrile were prepared via a convenient condensation polymerization procedure. The relationship among bisphenol structures, thermal properties and mechanical properties were investigated in details. By incorporating the thermally stable phenyl- s -triazine segment into the branched phthalonitrile's backbone, the overall T g (glass transition temperature) and T d (5% thermal degradation temperature) of the derived polymers were significantly improved. The resins were thermally cured to networks with 4,4′-diaminodiphenyl sulfone (DDS) as curing agent . The resulting networks exhibited high thermal resistance , indicated by T g surpassing 500 °C and T d as high as 575 °C. Additionally, the composites exhibited high mechanical properties and dielectric properties stability at 500 °C. The results suggested the merits of branched phthalonitrile polymers for applications in high-temperature resistant polymers and composites.
研究领域:
材料科学
·
高分子化学
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产品关联
DOI
高影响因子
POLYMER
·
2021
·
IF 4.43
Chong Gao,Hongbo Gu,Ai Du,Heng Zhou,Duo Pan,Nithesh Naik,Zhanhu Guo
Herein, we have reported that the polyaniline (PANI), as a polymeric catalyst, exhibits an outstanding efficiency for the curing of phthalonitrile resin as verified by differential scanning calorimetry (DSC) with a high enthalpy, in which the triazine structure is the dominating curing products as confirmed in the Fourier transform infrared (FTIR) spectra. Thermogravimetric analysis (TGA) and nanoindentation tests have been carried out to investigate the thermal and mechanical properties of the cured PANI/phthalonitrile resin. The results demonstrate that the PANI/phthalonitrile resin not only manifests a high char yield up to 24.7% at temperature of 850 °C in the air atmosphere, but also possesses an improved hardness that is 81.8% higher than that of regular small molecule of amine catalyst/phthalonitrile resin.
研究领域:
材料科学
·
化学工程
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DOI
高影响因子
POLYMER DEGRADATION AND STABILITY
·
2025
·
IF 7.4
Ya Xue,Ying Li,Fei Zhong,Zhongxiang Bai,Pan Wang,Kui Li,Fan Lei,Zhoukun He,Yang Yang,Wei Feng,Xulin Yang
Traditional benzoxazines are largely constrained by the dependence on non-renewable resources, solvent-based synthesis, and insufficient thermal resistance. This study presents a novel high-performance bio-based benzoxazine containing phthalonitrile (BZPN), synthesized via melt condensation using eugenol, 3-aminophenoxyphthalonitrile, and paraformaldehyde. The chemical formula of BZPN was validated by FTIR, ¹H and ¹³C NMR analyses. The curing of BZPN involves ring-opening polymerization of oxazine group and ring-forming polymerization from phthalonitrile unit, yielding polybenzoxazines and heteroaromatics respectively. Combined TG-DTG, TG-FTIR with TG-MS technique, the three-stage thermal pyrolysis mechanism of BZPN was proposed. The initial decomposition ( T dm1 =395 °C) occurs through the cleavage of C N, C O, and C C bonds in the polybenzoxazine, releasing NH₃, H₂O, CH₄, and CO₂. The second stage ( T dm2 =485 °C) involves the cleavage of C O and C C bonds in the heteroaromatic networks by releasing NH₃, H₂O, CH₄, and CO₂. The final carbonization stage ( T dm3 =615 °C) includes the transformation of highly aromatic compounds into graphite. With the facile solvent-less synthesis method and superior comprehensive properties (compressive strength: >220 MPa, T g : >375 °C, T d5 : >390 °C, and C y : 72 % at 800 °C), bio-based BZPN is a promising high-performance thermosetting resin for advanced industrial and engineering applications.
研究领域:
高分子化学
·
材料科学
·
有机合成
·
热分析
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产品关联
DOI
高影响因子
MOLECULES
·
2024
·Vol. 29
·期 23
·5668
·
IF 4.2
Dengxun Ren,Zexu Fan,Jiaqu Zhang,Yi Xu,Xianzhong Tang,Mingzhen Xu
To study the properties of cyclotriphosphazene (CTP)-containing phthalonitriles, a branched phthalonitrile containing CTP (CTP–PN) with self-catalytic behavior was designed and synthesized. The structure of CTP–PN was characterized by FT–IR (Fourier transform infrared spectroscopy), MS (mass spectroscopy), 1 H–NMR (proton nuclear magnetic resonance spectroscopy), and 13 C–NMR (carbon nuclear magnetic resonance spectroscopy). Then, the curing reaction of CTP–PN was studied using DSC (differential scanning calorimetry) and DRA (dynamic rheological analysis). The results show that the curing reaction of CTP–PN is initiated at 200 °C. Additionally, the change in the viscosity of CTP–PN as a function of the temperature was investigated. After curing at different temperatures, the generated structures were characterized by FT–IR. The fracture morphology and thermomechanical properties of cured CTP–PN were scanned and studied using SEM (scanning electron microscopy) and TMA (thermomechanical analysis), respectively. The results demonstrate that CTP–PN exhibits a smooth fracture surface and possesses a relatively low CTE (coefficient of linear thermal expansion) of approximately 25 ppm/°C at 285 °C. A T d5% (temperature at which 5% weight loss occurs) of as high as 405 °C can be obtained for cured CTP–PN, and its char yield at 800 °C exceeds 70% in N 2 . FT–IR and XPS (X-ray photoelectron spectroscopy) were used to study the thermal decomposition of cured CTP–PN, indicating that it remains stable below 350 °C. With an increasing temperature, there is decomposition first of CTP and P–NH–Ph and C–O–C bonds (>350 °C) and then nitrogen-containing aromatic heterocycles (>500 °C), ultimately resulting in the formation of P-containing residual char.
研究领域:
材料科学
·
化学
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产品关联
DOI
PubMed
高影响因子
Materials
·
2024
·Vol. 17
·期 17
·4411
·
IF 3.1
Cong Peng,Tao Luo,Zhanjun Wu,Shichao Li
The bisphenol A-type phthalonitrile (BAPH) was blended with the classic epoxy system E51/DDS to prepare the epoxy/phthalonitrile thermoset. The curing kinetics were investigated by differential scanning calorimetry (DSC) using the isoconversional principle, and the average activation energy (Eα) of the E51/DDS curing reaction was found to decrease from 87 kJ/mol to 68.6 kJ/mol. Combining the results of the rheological study, the promoting effect of phthalonitrile on the crosslink of epoxy/amine is confirmed. The curing reaction of the blended resin was characterized using FTIR, and the results showed that BAPH could react with DDS. The thermal behaviors of the thermosets were investigated via DMA and TGA. The glass transition temperature (Tg) is found to increase from 181 °C to 195 °C. The char yield increases from 16% to 59.6% at 800 °C in a N2atmosphere, which is higher than the calculated value based on the proportional principle. The AFM phase images show that there is no phase separation in the cured thermoset. The results imply that the cured epoxy/amine/phthalonitrile blend is probably a kind of copolymer. The real-time TG-MS indicated that the pyrolysis of the thermoset can be divided into two relatively independent stages, which can be assigned to the cleavage of the E51/DDS network, and the phthalocyanine/triazine/isoindoline, respectively.
研究领域:
材料科学
·
化学工程
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产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）