Synthesis And Properties Of Functional Helical Polymers

Helical is the essential attribute of the material, which is formed by the main chain continuous rotation rules. As the unique properties of helical materials, they draw more and more attention from a growing number of scientists. In addition to gain the structural material, chemists are now more prone to introduce the functional groups to the helical materials. In recent years, people focus on such work including (1) electrical activity helical materials: chiral switching spiral materials driven by electricity, chiral conductive spiral material; (2) optical activity helical material: spiral photochromic materials, optical information storage spiral material, spiral fluorescent probe material, the new LCD and LED spiral materials; (3) irritating the corresponding helical materials and (4) molecules, ion recognition helical materials and so on.In this paper, we adopted three methods to design and synthesize three types of functional spiral material, including (1) direct synthesis of helix polymers containing the chiral component, (2) non-chiral polymer induced spiralization by different solvents and (3) synthesis of chiral dopant-induced spiral compounds and made some meaningful results.(1) Synthesis and properties study of a polypyridine with binaphthyl moietie In this paper we synthesized a new chiral R-poly-6 polymer having pyridine and binaphthyl moietiefor by the Suzuki cross-coupling reaction, which was characterized with EA, IR, 1H-NMR and 13C-NMR spectroscopies. The CD and UV-Vis absorption spectra of the R-poly-6 result show it have the visible positive and negative Cotton effect in the 260-500 nm, which proof the R-poly-6 is a helical polymer.We attributed to each peak, and further studied the R-poly-6's indentification before and after annealing treatment on D(L) tartaric acid and (CH3CN)2PdCl2 by studying different peak peak movement and size changes of peak intensity in the CD spectra as well as R-poly-6's recognition on PdSO4 and CuCl2. In the third experiment, we found R-poly-6 have different effect capabilities with two kinds of ions, which indicates this polymer can be used as a potential chiral ion probe.(2) Synthesis of amphiphilic poly-carbazole and the study of the conformation spiralization induced by external environmental changesIn this paper we have synthesized the amphiphilic poly-carbazole 4-Poly-5 used the excellent optical properties hydrophobic carbazole as main part and the hydrophilic TEG as the side chain by Yamamoto-type Ullman polycondensation reaction and isolated different molecular weight of polymer used cycle of preparative column, whose structure and molecular weight were characterized by IR, NMR, GPC and MS tests. And then, we studied the conformational change of 4-Poly-5-a which the Number average molecular weight is 1.37×104 in the different ratios of mixed solvents of CHCl3 and DMSO.Studies have shown that polymer in the non-polar solvent CHCl3 showed random coil structure and the polymer conformation gradually turned into helical structure from random coil structure when DMSO/CHCl3 V/V is 40-50%. Such structural change is due to the hydrophobic force changes between the polymer and solvent.(3) Acid-induced synthesis of the different side aniline derivatives by chiral camphor sulfonic A series of aniline-based compounds with a different side were synthesizd using in-situ synthesis method with L-and D camphor sulfonic acid and hydrochloric acid as dopants We researched the electron-pushing side, electron-withdrawing hydrophilic side and electron-withdrawing hydrophobic side's effect on the molecular weight and structure of the compounds, ammonia dedoped compounds and second doped compounds by GPC and IR experments.The GPC results show the electron-pushing side aniline derivatives have the larger molecular weight and the electron-withdrawing hydrophilic side and electron-withdrawing hydrophobic side aniline derivatives have the smaller molecular weight. In addition, IR results show that the action between the dopant and polymer is also stronger in the electron-pushing side aniline derivatives polymers.(4) Chiral helical conformation study of the different side aniline derivatives synthesizd by chiral camphor sulfonic acid-inducedHelical conductive polyaniline and its derivatives have many unique excellent properties, in addition to electrical properties of polyaniline such as catalytic properties, electromagnetic shielding, electrochromic color and absorbing performance, they also have optical activity, which make them have the potential applications on the chiral recognition, membrane separation technology, bio-sensors, electrochemical polymerization and other fields. In this paper, we studied the chiral helical conformation of the different side aniline derivatives which were synthesized through chiral camphor sulfonic acid-induced by UV-Vis and CD experiments. The experiment results show that the electron-pushing ortho-substituent aniline derivatives and electron-withdrawing meta-substituent aniline derivatives can be induced the spiral of the main compound.Through the work of this paper, we have prepared three types helical materials with the main functional groups, which lay a certain functional materials foundation for the further study on the functional properties effect of the helical structure for such materials.