Research On Metalphthalocyanines/Polyarylene Ether Nitriles Functional Composites

Phthalocyanines（Pcs） have highly coplanar 18 electronic Ï€-bonded conjugate structures, and can coordinate with a number of metal ions to form metal phthalocyanine（MPcs）. Meanwhile, the axis and edge of phthalocyanine ring can link tomany kinds of special functional active substituents. The structural modificability makes these compounds have different functional properties. Besides, with the aid of covalent bond and intermolecular interaction force, Pcs can be made into phthalocyanine-containing polymers through autopolymerization or self-assembly. This process, not only further strengthens the unique physical and chemical properties of Pcs,but also equips them with good solubility and processability of polymers. In recent years, metalphthalocyanines（MPcs） have attracted much attention due to their excellent chemical stability and photoelectric properties, which give rise to their application in various domains, such as catalytic, conductive and dielectric materials, organic solar cell, optical materials and so on. Therefore, the design and synthesis of MPcs and their functional composites with shape-controlled and outstanding properties have become one of the hot research topics in recent years.In this paper, based on the above outstanding properties of MPcs, we prepared Fe-phthalocyanine containing flexible long branches chains oligomer/Fe₃O₄（NP-ph@Fe₃O₄） hybrids, amino phthalocyanine copper（NH₂-CuPc） and hyperbranchedphthalocyanine copper functional CNTs（HBCuPc-CNTs） nanoparticles,respectively. Meanwhile, these nanoparticles were subsequently used as the novel functional fillers or multi-scale reinforced material for preparation of dielectric and magnetic PEN composite films. The structure and properties of different MPcs functional nanoparticles and PEN composite films were systematically investigated.1. Firstly, the novel Fe-phthalocyanine containing flexible long branches chains oligomer/Fe₃O₄（NP-ph@Fe₃O₄） hybrids were synthesized from FeCl3·6H₂O as the iron source and 4-nonylphenoxy-1,2-dinitrilbenzene（NP-ph） through a simple solvent-thermal route. The composition, morphology and performance of the samples were studied by various testing methods. The results showed that the hybrids have good monodisperse orbicular structure and ferromagnetism. After the introductionof the Fe-phthalocyanine containing flexible long branches chains oligomer, the dielectric lossand magnetic loss of the hybrids achieve high-degree match, so that the hybrids show good electromagnetic microwave performance. For the S-3 sample, the maximum reflection loss（RL） value of electromagnetic properties achieved the peak value at-25.2dB at 17.4 GHz.2. The NP-ph@Fe₃O₄ hybrids prepared from a simple solvent-thermal route not only show excellent magnetic performance, but also present a very good dispersibility and stability in most of the polar organic solvents. Therefore, the PEN/NP-ph@Fe₃O₄films would have wider applications in magnetic materials fields due to its outstanding comprehensive performance.3. Then, high dielectric materials were developed by using MPcs. First, a novel aminophthalocyanine copper（NH₂-CuPc） with high dielectric constant was prepared and introduced into PEN matrix to improve the dielectric properties of the polymer. The as-prepared films were then under unidirectional hot-stretching in the oven to improve the dispersity of NH₂-CuPc in PEN matrix. In addition, due to the effectively suppressed the Dc leakage conductance by PEN insulating layer, the films show not only high permittivity but also low dielectric loss.4. Besides, novel HBCuPc covalently grafted CNTs were prepared from TPh and CNTs-CN via in situ polymerization. Thus, PEN/HBCuPc-CNTs dielectric composite films were prepared through solution casting method. The results showed that the HBCuPc-CNTs nanoparticles has good compatibility with PEN matrix and maintain uniform dispersion in the polymer matrix, thus the comprehensive performance of PEN composites were also greatly improved. Due to the stability of the chemical modified layer is far higher than that of physical adsorption layer, the permittivity of 9.0 wt%HBCuPc-CNTs composite film reached 51.7, and the tanδ is as low as 0.23. Moreover,the Umax of the composite is up to 2.87 J/cm3.5. Lastly, a novel core–shell structured magnetic CNTs was prepared by the self-assembly of phthalocyanines. After the introduction of HBCuPc, the complex permeability of the CNTs-Fe₃O₄ hybrids decreased, and the electromagnetic compatibility of the hybrids further increased, thus the CNTs-Fe₃O₄-HBCuPc hybrids exhibit excellent electromagnetic microwave absorbability. In addition, the bandwidth below-10.0 dB ranged from 5.5 to 18 GHz. Besides, the maximum RL value（-14.6 dB）of electromagnetic properties was achieved at 12.5 GHz. Besides, the CNTs-Fe₃O₄-HBCuPc hybrids can also serve as nanoparticle-reinforced fillers in PENmatrix, and make it equipped with excellent electromagnetic comprehensive performance.