Synthesis And Properties Of Novel Polyimides Containing Triptycene Trifluoromethyl And Iodine Functionalized Graphene

Polyimide(Polyimide, PI) is a kind of high performance polymer containing five or six element chain structure. Due to its outstanding chemical and physical properties, such as: heat resistance, resistance to chemical corrosion, low dielectric constant, which is widely used in aerospace, advanced composite materials, separation membrane, microelectronic devices and many other fields. As one of the representatives of heat-resistant polymer materials, since 1908, first reported so far, polyimide has undergone the development of more than a century, but due to its high production cost, there are high glass transition temperature, refractory insoluble, leads to difficult processing problem, limiting the development of polyimide material and the expansion of application fields. Studies show that the fluorine element, ether bond and three butterfly can improve the solubility of,. The through the molecular design and synthesis, first with fluorine, ether bond, and large volume of benzene ring structure is introduced into polyimide and strong C-F bond polarity and free volume increases the polyimide dissolved, optical transmission, reducing the dielectric constant; then the triptycene and fatty chain structure is introduced to the aromatic polyimide backbone, heat the excellent properties of polyimide, solubility has been improved to some extent, dielectric constant also showed a significant reduction in; finally iodo reduction of graphene oxide doped with fatty chain triptycene structure of polyimide, polyimide film with conductivity significantly improve. The main innovations are as follows:Firstly, from the molecular design of triptycene easily functionalized as the basis, we designed and synthesized novel dianhydride monomer 1,4- bis(3,4-carboxy phenyl carboxylic ethylene oxygen)- triptycene dianhydride BCEAD and 1,4- bis(3,4-carboxy phenyl carboxylic)- triptycene dianhydride BCPTD. Anthracene and p-benzoquinone as raw material by D-A reaction synthesised containing triptycene structure diketone, and under the acidic conditions the dionerearrangement get the triptycene hydroquinone, which actioned with ethylene carbonate under the conditions of K2CO3 in aldol condensation and introduced fatty chain of Triptycene-1,4- hydroquinone- bis(2-hydroxyethyl) ether THBHE. Under the condition of pyridine THBHE reactioned with Trimellitic anhydride chloride by nucleophilic substitution reactions for 1,4-bis(3,4-carboxy phenyl carboxylic ethylene oxygen based)- triptycene dianhydride. We synthesized 1,4- bis(3,4-carboxy phenyl carboxylic)-triptycene dianhydride in similar methods.The correctness of the structure was characterized by FT-IR, 1H NMR and 13 C NMR testing methods.Secondly,the synthesis of 1,4- bis(3,4-carboxy phenyl carboxylic ethylene oxygen)-triptycene dianhydride monomer and commercialization of ODPA respectively and diamine ODA, 1,3-BAPB, 1,4-BAPB and p-6FAPB polycondensation get the aliphatic chain triptycene polyimides. Through the performance test show that PI with triptycene, trifluoromethyl, aliphatic chain three structure has better permeability, solubility, low hygroscopicity,low dielectric constant, mechanical properties and heating resistance of PI. So the polyimide has a comprehensive integrated performance.Thirdly, cheap industrialization of anthracene and maleic anhydride as raw materials by D-A reaction synthesized dione. Under the acidic conditions the dione rearrangement has been higher yield of phenol, which reactioned with 2-chloro-5-nitro- trifluoromethyl benzene by nucleophilic substitution and abtained dinotro. In the Pd / C catalyst, dinotro was reductioned by hydrazine hydrate and obtained single containing fluorinediamine(9s,10s)-11,12-bis(4-amino-2-(trifluoromethyl)phenoxmethyl)-9,10-dihydrogen-9,10-ethanolanthracene.The structure is corrected by FT-IR, 1H NMR and 13 C NMR testing method.Fourth, with the increase of the amount of BATPEA, a series of polyimide were prepared by polymerization. That diamine containing fluorine BATPEA and ODPA and ODA make for. As control, ODPA was replaced by 6FDA, and another series of polyimide films were prepared. Through the performance test show that PI containing ether bond and trifluoromethyl and cyclohexane has a better through, fluorescence, solubility, low hygroscopicity and high dielectric constant. While improving the mechanical properties of PI, the heat resistance of PI is retained.Lastly, triptycene-1,4-hydroquinone-bis(2-hydroxyethyl)ether THBHE by nucleophilic substitution, reduction of nitro group obtained the diamine of the triptycene structure. The synthesised diamine and the commercialization dianhydride BPDA act as synthetic polymer precursors. We synthesised that adding different amounts R-I-Ph-GO /PI thin film materials. As a control, we used the same method, and replace RGO as R-I-Ph-GO. We also prepared the corresponding percentage of RGO/PI composite. Then we tested the moisture absorption, dielectric properties, thermal properties and mechanical properties of the two series of materials. We found that the addition of iodide to graphene significantly improved the conductivity of the polymer, while the tensile modulus, tensile strength and storage modulus of the polymer were also significantly improved.