GREEN CHEMISTRY
·
2024
·Vol. 26
·期 24
·12019-12033
·
IF 9.3
Yi Li,Qiancheng Liu,Qian Zhang,Xiaoxiao Li,Yang Yang,Pan Wang,Kui Li,Ying Li,Fei Zhong,Qi Liu,Yun Zheng,Xulin Yang,Peng Zhao
Phthalonitrile (PN) resins, renowned for their highly conjugated heteroaromatic N-rich structures, are exemplary precursors for the fabrication of porous materials. However, the conventional synthesis of PN is marred by the generation of the hazardous KNO2 by-product that poses significant environmental, safety, and health hazards. In this study, we introduce an innovative approach to PN synthesis, utilizing 4-chlorophthalonitrile as the starting material. This “utilize rather than create” strategy employs the reaction product (RPH) as the precursor and the by-product (KCl) as the template for the synthesis of porous carbon (RKC). The formation mechanism of RKC is elucidated through TGA/FTIR and TGA/MS analysis. The resultant RKCs exhibit exceptional characteristics suitable for supercapacitor applications, including hierarchical micro-/meso-/macropores, an extensive specific surface area, a high N-doping level, and diverse N species (N-6, N-5, N-Q). RKC@600 achieves a remarkable specific capacitance of 300 F g−1 at 1 A g−1 and demonstrates impressive cycling stability with a retention of 96.1% capacitance after 10 000 cycles at 10 A g−1. This research promotes the advancement of green and sustainable PN chemistry, driving forward the evolution of PN-based functional materials.
研究领域:
材料科学
·
能源化学
✓ 已验证
产品关联
DOI
高影响因子
Advanced Composites and Hybrid Materials
·
2023
·Vol. 6
·期 2
·1-12
·
IF 20.1
Zeng Junling,Xie Wenhao,Zhou Heng,Zhao Tong,Xu Ben Bin,Jiang Qinglong,Algadi Hassan,Zhou Zhenyu,Gu Hongbo
Herein, a nitrogen-doped graphite-like carbon material derived from hybrid phthalonitrile (PN) resin with controllable carbon microstructures including crystalline structures, hybridized carbon configurations, degree of disorder, and nitrogen species such as pyridinic N, pyrrolic N, and graphitic N has been manufactured by high-temperature annealing method. By simply altering these carbon microstructures through annealing temperature, the lowest resistivity of 1.76 Ω·cm at 290 K, the negative MR value of − 6.10% at a magnetic field of 9 T and negative permittivity over − 10 5 at low frequency are achieved in the semiconducting nitrogen-doped graphite-like carbon material. The results confirm the decreasing degree of disorder attained from Raman spectroscopy, the increasing ratio of sp 2 and sp 3 hybridized carbon, i.e., C( sp 2 )/C( sp 3 ), from X-ray photoelectron spectroscopy (XPS), and the rise of charge carrier mobility with increasing the magnetic field from Hall-effect measurement is responsible for the negative MR effect in this nitrogen-doped graphite-like carbon material. The negative permittivity is attributed to the plasma oscillation with delocalized charge carriers by the Drude model and the greatly increasing graphitic N in the carbon microstructures. This work opens a new insight for the applications of carbonized PN resins in the electronic device field.
研究领域:
材料科学
·
电子工程
✓ 已验证
DOI
高影响因子
JOURNAL OF MATERIALS SCIENCE
·
2025
·Vol. 60
·期 47
·24905-24921
·
IF 3.9
Xie Meina,Song Kunpeng,He Jiyu,Yang Rongjie,Chen Pengwan
Cross-linking phthalonitrile (PN) monomers readily forms substances with high thermal stability, and POM-catalyzed carbonization is a promising method to enhance polymer flame retardancy. In this study, ethoxyimidazole-modified phthalonitrile (EIPN) was synthesized and combined with H 3 PMo 12 O 40 ·nH 2 O to form the protonated salt [EIPN] 3 PMo 12 O 40 . Subsequently, TPU/EIPN and TPU/[EIPN] 3 PMo 12 O 40 composites were prepared. The results showed that both EIPN and [EIPN] 3 PMo 12 O 40 facilitated self-accelerating thermal crosslinking, leading to the formation of triazine and phthalocyanine rings with high thermal stability. TPU composites containing 3 wt% EIPN and [EIPN] 3 PMo 12 O 40 exhibited excellent flame retardant properties, with limiting oxygen index (LOI) of 22.2% and 21.6%, respectively. The peak heat release rate (pHRR) of TPU/3%[EIPN] 3 PMo 12 O 40 was reduced by 28.3% compared to TPU, while the total smoke release (TSR) of TPU/3%EIPN reduced by 22.2% in comparison to TPU. Notably, [EIPN] 3 PMo 12 O 40 demonstrated dynamic mechanical properties characterized by low energy dissipation and an extended fatigue life. This study offers new insights into using phthalonitrile cross-linking in flame-retardant TPU.
研究领域:
材料科学
·
高分子化学
·
消防安全工程
·
热稳定性
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF APPLIED POLYMER SCIENCE
·
2015
·Vol. 132
·期 39
·
IF 1.768
Fenghua Zhao,Ruojin Liu,Xiaoyan Yu,Kimiyoshi Naito,Xiongwei Qu,Qingxin Zhang
A phthalonitrile-substituted phosphonitrilic monomer has been synthesized from phosphonitrilic chloride trimer and then polymerized with addition of 4-(hydroxylphenoxy)phthalonitrile (HPPN). The chemical structures of the phosphonitrilic monomer and polymer were characterized by Fourier Transform Infrared spectroscopy (FT-IR) and proton Nuclear Magnetic Resonance spectroscopy ( 1 H NMR). Curing behaviors and thermal stabilities of the polymer were investigated through differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Analysis showed that the monomer has large processing temperature window and good thermal stability. Apparent activation energy, initial curing temperature ( T i ), curing temperature ( T p ), and termination curing temperature ( T f) of the phosphonitrilic polymer were explored. Dynamic mechanical analysis (DMA), glass transition temperature ( T g ) were studied, and limiting oxygen index (LOI) were estimated from the van Krevelen equation, which indicates the polymer process high modulus and good flame retardance. Micro-scale combustion calorimetry (MCC) was also used for evaluating the flammability of the polymers. Postcuring effects were explored, showing excellent thermal and mechanical properties with postcuring. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132 , 42606.
研究领域:
高分子科学
·
材料化学
·
热分析
·
阻燃材料
·
高性能聚合物
✓ 已验证
DOI
高影响因子
POLYMER
·
2019
·
IF 3.771
Yue Han,Donghao Tang,Guangxing Wang,Youlan Zhang,Ying Guo,Heng Zhou,Wenfeng Qiu,Tong Zhao
Soluble hyperbranched poly(arylene ether nitrile)s end-capped by either hydroxyl (HBPAEN-OHs) or phthalonitrile groups (HBPAEN-PNs) were synthesized via nucleophilic substitution reactions , where activated carbon supported calcium oxide was used as the catalyst to avoid crosslinking at high conversion. In order to evaluate their potential application in phthalonitrile resins, these hyperbranched polymers were blended with 1,3-bis(3,4-dicyanophenoxy)benzene and 4-(4-aminophenoxy)phthalonitrile, then cured into polymers. Curing mechanisms of different prepolymers were proposed and compared, and processability, thermal and mechanical properties were characterized. The introduction of HBPAEN-OHs was found to postpone the curing, while thermal and mechanical properties were compromised. On the contrary, the usage of HBPAEN-PNs was beneficial to both processability and thermal properties. More importantly, the impact strength for polymers containing HBPAEN-PN could be as high as 12.92 kJ m −2 , indicating such resin could be potentially applied as high temperature structural composite matrices. In addition, the toughening mechanism was proposed and discussed.
研究领域:
材料科学
·
高分子化学
✓ 已验证
产品关联
DOI
高影响因子
ECS Journal of Solid State Science and Technology
·
2015
·Vol. 5
·期 2
·P21
·
IF 1.558
Bin Hu,Wen Luo,Lin Jin,Zengchen Liu,Mengnan Wang,Liuyang Zhou,Chunyang Li
Two novel carbazole-3, 4-ethoxylenedioxythiophene (EDOT) derivatives containing acceptor groups such as benzonitrile and phthalonitrile were synthesized and characterized. Both the monomers could be electrochemically polymerized and form stable electroactive polymer films. Spectroelectrochemical technique were performed to investigate the electrochemical and optical changes of the resulting polymer films, multi-electrochromic properties upon different applied potentials suggested the effect of the benzonitrile and phthalonitrile units and their potential applications in electrochromic device. Furthermore, scanning electron micrographs (SEM) were used to study the microstructure morphology of polymer films.
研究领域:
材料科学
·
电化学
·
高分子化学
✓ 已验证
产品关联
DOI
高影响因子
THERMOCHIMICA ACTA
·
2017
·
IF 2.236
Weifeng Peng,Yang Liu,zhengzhou Liu,Zheng Lu,Jianghuai Hu,Ke Zeng,Gang Yang
Phthalonitrile and alicyclic imide moiety blends were obtained by mechanical mixing, and the curing behaviors and kinetics parameters of the phthalonitrile/alicyclic imide moiety systems were investigated by non-isothermal differential scanning calorimetry (DSC). The results showed that an apparent autocatalytic model dα/dt = k(T)α m (1 − α) n can be determined to describe the systems, and the apparent activation energy of 3BOCN/CC-55, 3BOCN/CC-73 and 3BOCN/HCC-55 are 105.9, 120.6 and 83.4 kJ/mol with not much different reaction orders 1.67, 1.49 and 1.56, respectively. The conversions which are approximately 0.36, 0.41 and 0.40 corresponding to the maximum reaction rate values of 3BOCN/CC-55, 3BOCN/CC-73 and 3BOCN/HCC-55 are experimentally determined, respectively, which are in good agreement with the fitting values.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
HIGH PERFORMANCE POLYMERS
·
2022
·
IF 1.73
Mehdi Derradji,Oussama Mehelli,Karim Khiari,Slimane Abdous,Sarah Soudjrari,Abdeldjalil Zegaoui,Noureddine Ramdani,Wenbin Liu,Mohamadou Al Hassan
Benzoxazine containing phthalonitrile, as one of the most advanced high performance thermosetting resin, has gained a lot of attention in the last decades. Indeed, the combination of the thermally activated ring-opening polymerization of the benzoxazine and the cyano addition reaction of the phthalonitrile allows the development of robust polymeric networks. Following this path, a renewable natural resource, vanillin, was used to develop a new benzoxazine containing phthalonitrile thermosetting system. The newly developed monomers present the advantage of a simple synthesis process along with an autocatalytic polymerization mechanism. The molecular structures of the synthesized monomers were characterized by Fourier transform infrared spectroscopy (FTIR) and proton nuclear magnetic resonance spectroscopy (1H NMR). The curing behavior was assessed by differential scanning calorimetry (DSC). The newly developed monomers were then reinforced with a silane surface modified basalt fibers (BFs) allowing the preparation of a high performance green composite. The silane surface modification of the BFs was confirmed by FTIR and thermogravimetric analysis (TGA). The tensile and bending tests highlighted the remarkable mechanical properties of the developed green composite. Finally, the scanning electron microscopy (SEM) was used to study the mechanism of stress transfer between the matrix and the fillers. Overall, the developed green composite can be seen as a promising substitute to composites made from glass fibers.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
POLYMER
·
2022
·
IF 4.432
Xian He,Jiayue Qi,Menghao Chen,Jiangbo Lv,Hang Xiao,Jianghuai Hu,Ke Zeng,Gang Yang
Nucleophilic reactions , as extensive and easily implementable reactions in organic chemistry , play a significant role in the molecular design of organic compounds and polymer materials. In current sustainable development strategies, nucleophilic reactions are also being shifted towards green chemistry. In this paper, phthalonitrile (PN) resin, a thermoset prepared by nucleophilic substitution reaction , was selected for a case study to investigate the application and reusability of the ‘green solvent’ dimethyl carbonate (DMC) in the nucleophilic substitution reaction. This research employed naturally existing vanillin and tyramine for the synthesis of a fully bio-based bisphenol bearing a Schiff base structure (VTBP). Then VTBP was converted to a novel bio-based PN (VTPN) through a nucleophilic substitution reaction in DMC, and the DMC was recovered and reused through a rotary evaporation . The structure, curing behavior, and performance of the cured resin of the synthesized VTPN were characterized. The results suggest that the Schiff base may promote and participate in the crosslinking of nitrile , with a relatively high performance achieved under moderate curing conditions. This study provides a new green implementation scheme for high-performance polymers prepared through nucleophilic reactions, as well as for the high-performance and efficient utilization of widely existing bio-based aldehydes and amines.
研究领域:
有机化学
·
高分子材料科学
·
绿色化学
✓ 已验证
产品关联
DOI
高影响因子
HIGH PERFORMANCE POLYMERS
·
2022
·
IF 1.73
Sarah Soudjrari,Mehdi Derradji,Bouchra Amri,Khawla Djaber,Oussama Mehelli,Sana Tazibet,Slimane Abdous,Noureddine Ramdani,Wenbin Liu,Azzedine Khadraoui
Benzoxazine containing phthalonitrile, as one of the most advanced high performance thermosetting resin, has gained a lot of attention in the last decades. Indeed, the combination of the thermally activated ring-opening polymerization of the benzoxazine and the cyano addition reaction of the phthalonitrile allows the development of robust polymeric networks. Following this path, a renewable natural resource, vanillin, was used to develop a new benzoxazine containing phthalonitrile thermosetting system. The newly developed monomers present the advantage of a simple synthesis process along with an autocatalytic polymerization mechanism. The molecular structures of the synthesized monomers were characterized by Fourier transform infrared spectroscopy and proton nuclear magnetic resonance spectroscopy . Thermal properties were also characterized by differential scanning calorimetry and thermogravimetric analysis . Typically, the newly developed monomers showed excellent thermal stability with starting decomposition temperatures over 496.4°C with a char yield at 800°C of about 80.7%. The thermomechanical properties were investigated by dynamic mechanical analyzer and the fractured surfaces were studied by scanning electron microscopy Globally, the newly developed partially bio polymer showed outstanding thermal resistance along with excellent thermomechanical properties.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
IRANIAN POLYMER JOURNAL
·
2025
·
IF 2.8
Zhu Guanglai,Xu Chao,Xu Ziyi,Yu Yitao,Sun Cuicui,Zhuang Haihua,Ma Baichang,Hou Yantao,Li Bing,Wang Zhenhua,Dai Caifeng
Phthalonitrile (PN) resins are high-performance thermosetting polymers recognized for their exceptional thermal stability and flame resistance, making them attractive candidates for aerospace, electronics, and high-temperature structural applications. However, their broader adoption is hindered by two primary challenges: the high melting point of PN precursors and the volatility of conventional curing agents, which complicate processing and raise safety concerns. Despite ongoing research, effective strategies that simultaneously address these issues while enhancing the overall performance of PN resins remain limited. In this study, we introduce a novel self-catalyzing curing agent, 4-(7-amino-1-naphthoxy) phthalonitrile (ANP), which functions both as a precursor and curing agent. The presence of amino and naphthoxy groups promotes efficient curing without the need for external catalysts, thereby expanding the processing window. Additionally, amino and cyano groups act as reactive sites and flexibilizers, enhancing the properties of bisphenol A-based PN (AFPN) resin systems. Thermal analysis revealed that the ANP-modified resin exhibits outstanding thermal and thermo-oxidative stability, with a 5% weight loss temperature ( T 5% ) exceeding 450 °C and a glass transition temperature ( T g ) above 439 °C. Vector network analysis further demonstrated excellent dielectric properties, with a dielectric constant ( D k ) of 3.15 and a dissipation factor ( D f ) of 0.017 at 9.05 GHz. These findings indicate that ANP effectively overcomes key limitations of conventional PN resins. As a multifunctional curing agent, ANP shows significant potential for the development of advanced PN-based composites in aerospace, electronic packaging, and microelectronic applications. Graphical abstract
研究领域:
材料科学
·
高分子化学
·
化学工程
·
航空航天工程
·
电子封装
✓ 已验证
产品关联
DOI
高影响因子
REACTIVE & FUNCTIONAL POLYMERS
·
2017
·
IF 3.151
Abdul Qadeer Dayo,Xin-man Cao,Wan-an Cai,Sha Song,Jun Wang,Abdeldjalil Zegaoui,Mehdi Derradji,Yi-le Xu,An-ran Wang,Wen-bin Liu,Lin-dan Gong
The benzophenone-center bisphenol-A containing phthalonitrile monomer (BBaph) was successfully produced by a nucleophilic substitution reaction of 4,4′-difluorobenzophenone with 4-nitrophthalonitrile and bisphenol-A in the presence of potassium carbonate . The chemical structure of the synthesized monomer was confirmed by 1 H nuclear magnetic resonance ( 1 H NMR), 13 C NMR, and Fourier transform infrared spectroscopy (FTIR). The curing study of monomer was evaluated by the FTIR and DSC curves. The poly(BBaph) was subjected to gamma-ray irradiation with 100 kGy dose of 60 Co gamma radiation. The variation in chemical structure, mechanical, thermomechanical and thermal properties of poly(BBaph) was evaluated by FTIR, flexural, dynamic mechanical analysis (DMA), and thermogravimetric analysis (TGA), respectively. All results confirmed very minute deviation in the estimated properties before and after radiation. The BBaph monomer was blended with typical mono-functional benzoxazine ( P-a ) in different weight ratios. The DSC , DMA, and TGA tests were performed to study the properties of copolymers . The high glass transition temperature (164–227 °C), and stiffness values (2.72–3.03 GPa) was observed for the copolymers . The thermal stability was also improved after the loading of BBaph in P-a , recorded values were in the range of 367–408 °C, and 46.1–58.7% for 5% weight loss temperature and char yield at 800 °C, respectively.
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）