Versatile Synthesis of Carbon Materials using Protic Ionic Liquids and Salts as Precursors

Carbon materials (CMs) hold immense potential for applications across a wide range of fields. However, current precursors often confront limitations such as low heteroatom content, poor solubility, or complicated preparation and post-treatment procedures. Our research has unveiled that protic ionic liquids and salts (PILs/PSs), generated from the neutralization of organic bases with protonic acids, can function as economical and versatile small-molecule carbon precursors. The resultant CMs display attractive features, including elevated carbon yield, heightened nitrogen content, improved graphitic structure, robust thermal stability against oxidation, and superior conductivity, even surpassing that of graphite. These properties can be elaborate modulated by varying the molecular structure of PILs/PSs. In this Personal Account, we summarize recent developments in PILs/PSs-derived CMs, with a particular focus on the correlations between precursor structure and the physicochemical properties of CMs. We aim to impart insights into the foreseeable controlled synthesis of advanced CMs.     

Preparation and characterization of photo-decomposable ester-containing semi-alicyclic polyimide alignment layers for potential applications in in-plane switching thin-film transistor liquid crystal display devices

Poly(amic acid)s (PAAs) alignment agents have been prepared from the alicyclic dianhydrides, including 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA, I), 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride (DMCBDA, II), and ester-linked aromatic diamines, including 4-aminophenyl-4′-aminobenzoate (APAB, a) and bis(4-aminophenyl)terephthalate (BPTP, b), respectively. The derived PAAs, including PAA-I_a (CBDA-APAB), PAA-I_b (CBDA-BPTP), and PAA-II_a (DMCBDA-APAB) exhibited the preferable molecular weights, while the PAA-II_b (DMCBDA-BPTP) showed the low one due to the low polymerization reactivity both for the DMCBDA dianhydride and the BPTP diamine. All the PAA solutions except PAA-II_b were adopted as the alignment components to fabricate liquid crystal (LC) minicells with a mode of in-plane switching (IPS). The polyimides (PI) alignment layers derived from the thermal dehydration reaction of the PAA precursors at 230°C for 30 min showed good alignments effects to the LC molecules, which exhibited the pretilt angles (θ_p) from 0.09 to 0.15° after being exposed by the linear polarized ultraviolet light sources with the wavelength of 254 nm. In addition, the PI alignment layers afforded good optoelectronic features to the minicells, including the voltage holding ratio values over 97% at room temperature, and the residual direct circuit voltages lower than 1.0 V. The anchoring energy results indicated that the PI-II_a (DMCBDA-APAB) alignment layer showed the highest interaction with the LC molecules, and thus exhibited the highest threshold voltage (V_th) in the voltage-transmittance (V-T) measurements for the minicells.     

New organosoluble polyimides with low dielectric constants derived from bis[4-(2-trifluoromethyl-4-aminophenoxy)phenyl] diphenylmethylene

A new kink diamine with trifluoromethyl group on either side, bis[4-(2-trifluoromethyl-4-aminophenoxy)phenyl]diphenylmethane (BTFAPDM) , was reacted with various aromatic dianhydrides to prepare polyimides via poly (amic acid) precursors followed by thermal or chemical imidization. Polyimides were prepared using 3,3′, 4,4′-biphenyltetracarboxylic dianhydride(1), 4,4′-oxydiphthalic anhydride(2), 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (3), 4,4′-sulfonyldiphthalic anhydride(4), and 4,4′-hexafluoroisopropylidene-diphathalic anhydride(5). The fluoro-polyimides exhibited low dielectric constants between 2.46 and 2.98, light color, and excellent high solubility. They exhibited glass transition temperatures between 227 and 253°C, and possessed a coefficient of thermal expansion (CTE) of 60-88 ppm/°C. Polymers PI-2, PI-3, PI-4, PI-5 showed excellent solubility in the organic solvents: N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), pyridkie and tetrahydrofuran (THF). Inherent viscosity of the polyimides were found to range between 0.58 and 0.72 dLg-1. Thermogravimetric analysis of the polyimides revealed a high thermal stability decomposition temperature in excess of 500°C in nitrogen. Temperature at 10 % weight loss was found to be in the range 506-563°C and 498-557°C in nitrogen and air, respectively. The polyimide films had a tensile strength in the range 75-87 MPa; tensile modulus, 1.5-2.2 GPa; and elongation at break, 6-7%.