Solid-state Polymerization Method Research Articles

Modulating the Band Structure of Metal Coordinated Salen COFs and an In Situ Constructed Charge Transfer Heterostructure for Electrocatalysis Hydrogen Evolution.

A series of crystalline, stable Metal (Metal = Zn, Cu, Ni, Co, Fe, and Mn)‐Salen covalent organic framework (COF)EDA complex are prepared to continuously tune the band structure of Metal‐Salen COFEDA, with the purpose of optimizing the free energy intermediate species during the hydrogen evolution reaction (HER) process. The conductive macromolecular poly(3,4‐ethylenedioxythiophene) (PEDOT) is subsequently integrated into the one‐dimensional (1D) channel arrays of Metal‐Salen COFEDA to form heterostructure PEDOT@Metal‐Salen COFEDA via the in situ solid‐state polymerization method. Among the Metal‐Salen COFEDA and PEDOT@Metal‐Salen COFEDA complexes, the optimized PEDOT@Mn‐Salen COFEDA displays prominent electrochemical activity with an overpotential of 150 mV and a Tafel slope of 43 mV dec−1. The experimental results and density of states data show that the continuous energy band structure modulation in Metal‐Salen COFEDA has the ability to make the metal d‐orbital interact better with the s‐orbital of H, which is conducive to electron transport in the HER process. Moreover, the calculated charge density difference indicates that the heterostructures composed of PEDOT and Metal‐Salen COFEDA induce an intramolecular charge transfer and construct highly active interfacial sites.

Facile synthesis of poly(BODIPY)s via solid state polymerization and application in temperature sensor

Several 3,5-dibromo substituted BODIPY (4,4′-Difluoro-4-bora-3a,4a-diaza-s-indacene) derivatives were rationally designed and investigated as potential candidates to perform solid state polymerization (SSP). Compared with the traditional systems of thiophene and diacetylene families, which were successfully applied in SSP, SSP has been expanded to the BODIPY system in this article. In addition, crystallographic data of BODIPY derivative was derived to analyze the reasonable path of SSP, which could further explore the mechanism of SSP. Furthermore, the relationship between fluorescence intensity of BODIPY after SSP and temperature was established, which could apply this material in temperature fluorescence sensor with outstanding relative sensitivity (Sr) of 0.898% K−1. Our work has been proved to pave the way to explore more conjugated systems by using SSP method and enrich SSP database systematically.

Solid-state synthesis of conjugated doped poly(3,4-ethylenedioxythiophene): An effective adsorbent for selective anionic dye removal

In this work, we report the adsorption studies of dyes using as-prepared doped poly(3,4-ethylenedioxythiophene) (PEDOT). The conjugated polymer PEDOT was prepared by the solid-state polymerization method and used as an effective adsorbent for the removal of various dyes from aqueous solution. It was found that the as-prepared PEDOT adsorbs selective anionic dyes, whereas no significant adsorption was observed for cationic dyes. The effect of concentration of eriochrome black T (EBT) dye on time-dependent adsorption was studied. Like doped PEDOT, de-doped PEDOT was examined with different concentrations of EBT dye solutions and observed poor adsorption. The adsorption kinetics and isotherms for doped and de-doped PEDOT were studied. The morphology and elemental composition of doped PEDOT before and after adsorption were analyzed by scanning electron microscopy and energy-dispersive X-ray, respectively. Further, the effectiveness of as-prepared doped polymer PEDOT as an adsorbent for EBT dye from organic solvents (ethanol, DMSO, acetonitrile and DMF) was carried out.

Synthesis, characterization of Ag@PANI core-shell nanostructures using solid state polymerization method

One-step reaction has been developed to obtain Ag@Polyanilin (Ag@PANI) core-shell nano-structures. Aniline sulphate was oxidized by silver nitrate using solid-state polymerization method at room temperature. The structure and morphology of the core-shell were characterized by the Fourier transform infrared (FTIR) spectra, Ultraviolet-Visible (UV–Vis) absorption spectra, X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The XRD patterns displayed both the broad amorphous polymeric and sharp metallic peaks. The results from TEM and SEM images showed that the nano-composites have coreshell structures. The changes occurring in the structure of PANI are discussed on the basis of infrared and UV-Vis spectroscopy. The spectra revealed the formation of the nano-composites.

Highly flexible electrospun carbon/graphite nanofibers from a non-processable heterocyclic rigid-rod polymer of polybisbenzimidazobenzophenanthroline-dione (BBB)

Development of mechanically flexible carbon nanofibers is highly desired for the applications in modern flexible electronics and energy storage devices. This work reports the manufacture and characterization of highly flexible carbon nanofibers (CNFs) and graphitic carbon nanofibers (GCNFs) from a non-processable heteroaromatic rigid-rod polymer, polybisbenzimidazobenzophenanthroline-dione (BBB). The flexible CNFs/GCNFs were prepared by a newly developed method of electrospun nanofiber template solid-state polymerization, followed by carbonization/graphitization. In specific, BBB nanofibers were prepared first by the nanofiber template solid-state polymerization method using polyimide as template by electrospinning and heat treatment (500 °C). Subsequently, CNFs/GCNFs were obtained through carbonization under different temperatures of 1200–2700 °C. SEM, HRTEM, Raman spectroscopy, and XRD were used to characterize the morphologies and microstructures. Intriguingly, the BBB-derived CNFs/GCNFs presented extremely good mechanical flexibility that resisting to readily bending, folding, and kneading. Hence, this newly developed extremely flexible BBB-derived CNFs/GCNFs with such good performance could have great potential applications such as using as electrode materials for flexible electrochemical devices.

Chemical oxidative and solid state synthesis of low molecular weight polymers for organic field effect transistors

Solution processability of the precursor molecules is a major issue owing to their limited solubility for the synthesis of conjugated polymers. Therefore, we favour the solvent free solid state chemical oxidative polymerization route for the synthesis of diketopyrrolopyrrole (DPP) based donor-acceptor (D-A) type conjugated polymers. D-A type polymer Poly(S-OD-EDOT) which contains DPP coupled with EDOT donor units is synthesized via solid state polymerization method. The polymer is employed as an active layer for organic field-effect transistors to measure charge transport properties. The Polymer shows good hole mobility 3.1 × 10−2 cm2 V−1 s−1, with a on/off ratio of 1.1 × 103.

Solid-state method for incorporation of lead sulfide nanoplates in poly(3,4-ethylenedioxythiophene) matrix as NIR materials

We investigate the direct incorporation of lead sulfide nanoplates (PbS-NP) in poly(3,4-ethylenedioxythiophene) (PEDOT) matrix without any additives. The PbS-NP was synthesized by using an ultrasonic assistance simple method and composite of them with PEDOT was carried out by a simple solid-state polymerization method. The TEM images, X-ray diffraction patterns and absorption spectra confirm the incorporation of PbS-NP in PEDOT matrix. The XRD pattern showed that the prepared PbS-NPs are crystalline in cubic rock salt structure with 8 nm average grain size. The UV/Vis/NIR spectrum of PEDOT/PbS-NP nanocomposite shows a characteristic peak at NIR region and a large blue shift rather than bulk lead sulfide. This shift confirms synergetic effect between PEDOT matrix and PbS-NPs and presence of quantum confinement effect for prepared PbS-NP. In addition, this characteristic peak is very much dependent on the PbS-NP concentration and can be used for design tunable NIR materials.

Synthesis of functionalizable derivatives of 3,4‐ethylenedioxythiophene and their solid‐state polymerizations

ABSTRACTFour polythiophenes based on poly(3,4‐ethylenedioxythiophene) (PEDOT) framework have been successfully prepared by the facile thermal activated solid‐state polymerization (SSP) process from their corresponding dibromothiophene derivatives, which were efficiently obtained using our improved methodology. Rates of polymerizations of these precursors were varied and most of the processes were incomplete under the reaction condition chosen for the synthesis. Raising the reaction temperature of the SSP further advanced the polymerization progress and improved the conductive properties of the polymer. The polymer of 3,4‐ethylenedioxythiophene‐methanol (EDTM) and its two related derivatives with functionalizable groups were prepared for the first time by the SSP method. The process and these new SSP‐derived polymers could help solving the fabrication difficulty and expand the scope of their applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42233.

Synthesis and investigation of novel thiophene derivatives containing heteroatom linkers for solid state polymerization

Several thiophene derivatives containing different heteroatom linkers were rationally designed, synthesized and studied as potential candidates for solid state polymerization (SSP). Due to the flexible short single heteroatom linkers, these monomers may rotate freely under heating to meet the requirement needed for SSP. Meanwhile, our novel design strategy has been proved to be an amazing protocol and will pave the way to explore more systems in the polythiophene family by using such a facile SSP method.

Incorporation of Isosorbide into Poly(butylene terephthalate) via Solid-State Polymerization

The biomass-based monomer isosorbide was incorporated into poly(butylene terephthalate) (PBT) by solid-state polymerization (SSP) using the macrodiol monomer BTITB-(OH) 2, which consists of isosorbide (I), terephthalic acid (T), and 1,4-butandiol (B) residues. This macromonomer can be synthesized by a simple one-pot, two-step reaction. Polymers with number-average molecular weights up to 100,000 g x mol (-1) were readily synthesized from various ratios of PBT/BTITB-(OH) 2. Their molecular weights, thermal properties, and colors were compared with corresponding copolyesters that were obtained by melt polycondensation. We found that T m, T c, and especially T g were superior for materials that were obtained by SSP. This is ascribed to differences in the microstructures of both types of copolyesters; the SSP products exhibit a more blocky structure than do the more random melt-polymerized counterparts. The SSP method resulted in much higher molecular weights and much less colored polymers, and it seems to be the preferred route for incorporating biobased monomers that exhibit limited thermal stability into engineering plastics.

Comparative studies of solid-state synthesized poly(o-methoxyaniline) doped with organic sulfonic acids

Poly(o-methoxyaniline) (POMA) salts doped with organic sulphonic acids (methanesulphonic acid, p-toluenesulphonic acid and dodecylbenzenesulphonic acid) were firstly synthesized by using solid-state polymerization method. The polymers were characterized by Fourier transform Infrared (FTIR) spectra, ultraviolet visible (UV–vis) spectrometry, X-ray diffraction (XRD), Cyclic Voltammetry (CV), and conductivity measurements. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were done to study the morphologies of POMA salts. The results showed that the POMA doped with methanesulphonic acid displayed higher doping level and conductivity. On the contrary, POMA doped with dodecylbenzenesulphonic acid was lower at doping level and conductivity. In accordance with these results, the electrochemical activity was also found to be lower in dodecylbenzenesulphonic acid doped POMA. The results also revealed that the particles of POMA salts have the average size of less than 100 nm.

Comparative studies of solid-state synthesized polyaniline doped with inorganic acids

Polyaniline (PANI) salts doped with inorganic acids (HCl, H 2SO 4 and H 3PO 4) were directly synthesized by using solid-state polymerization method. The FTIR spectra, UV–vis absorption spectra and X-ray diffraction patterns were used to characterize the molecular structures of the PANI salts. Voltammetric study was done to investigate the electrochemical behaviors of all these PANI salts. The PANI salts were affected by varying the protonation media (HCl, H 2SO 4 and H 3PO 4). The FTIR and UV–vis absorption spectra revealed that all PANI salts contained the conducting emeraldine salt phase at different oxidation state. The crystallinity of PANI doped with HCl was better than those doped with H 2SO 4 and H 3PO 4. The conductivity of the PANI doped with HCl is the highest among the inorganic acid doped PANI.