Room temperature synthesis of perylene diimides facilitated by high amic acid solubility

A novel protocol for the synthesis of perylene diimides (PDIs), by reacting perylene dianhydride (PDA) with aliphatic amines is reported. Full conversions were obtained at temperatures between 20 and 60˚C,...

Eco-Friendly Water-Processable Polyimide Binders with High Adhesion to Silicon Anodes for Lithium-Ion Batteries

Silicon is an attractive anode material for lithium-ion batteries (LIBs) because of its natural abundance and excellent theoretical energy density. However, Si-based electrodes are difficult to commercialize because of their significant volume changes during lithiation that can result in mechanical damage. To overcome this limitation, we synthesized an eco-friendly water-soluble polyimide (W-PI) precursor, poly(amic acid) salt (W-PAmAS), as a binder for Si anodes via a simple one-step process using water as a solvent. Using the W-PAmAS binder, a composite Si electrode was achieved by low-temperature processing at 150 °C. The adhesion between the electrode components was further enhanced by introducing 3,5-diaminobenzoic acid, which contains free carboxylic acid (–COOH) groups in the W-PAmAS backbone. The –COOH of the W-PI binder chemically interacts with the surface of Si nanoparticles (SiNPs) by forming ester bonds, which efficiently bond the SiNPs, even during severe volume changes. The Si anode with W-PI binder showed improved electrochemical performance with a high capacity of 2061 mAh g−1 and excellent cyclability of 1883 mAh g−1 after 200 cycles at 1200 mA g−1. Therefore, W-PI can be used as a highly effective polymeric binder in Si-based high-capacity LIBs.

Processable poly(ether ether ketone imide)s

New aromatic poly(ether ether ketone imide)s, [PEEKimide]s, were synthesized successfully from 1,3-bis-4′-(4″-aminophenoxy benzoyl) benzene and various commercially available aromatic dianhydrides, such as pyromellitic dianhydride (PMDA), 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 3,3′,4,4′-biphenyl tetracarboxylic dianhydride (BPDA), 4,4′-oxydiphthalic anhydride (OPDA) and 4,4′-(hexafluro isoproylidene) diphthalic anhydride (HFDA), by two step polycondensation method. These PEEKimides were characterized by FT-IR, solubility in organic solvents, inherent viscosity, DSC, TGA and WXRD. Inherent viscosities of the precursor poly(ether ether ketone amic acid)s were in the range of 0.23–0.40 dl/g in DMF, indicating formation of moderate to high molecular weights. These poly(ether ether ketone imide)s showed good solubility in polar aprotic solvents such as N,N-dimethylacetamide (DMAc), N-methyl 2-pyrrolidone (NMP), N,N-dimethylformamide (DMF) and dimethyl sulphoxide (DMSO) and had glass transition temperatures in the range 245–279°C. Poly(ether ether ketone imide)s showed no weight loss below 280°C; temperatures for 10% weight loss (T10) were in the range of 406–483°C and char yields at 800°C were 17–34%, indicating their good thermal stability. All these poly(ether ether ketone imide)s were amorphous in nature, as per patterns of WXRD which exhibited diffuse broad halos at (2θ = 10–30°) and amorphous nature was reflected in polymer’s good solubility in common organic solvents.

Novel Polyimide-block-poly(dimethyl siloxane) copolymers: Effect of time on the synthesis and thermal properties

Polyimide-block-poly(dimethyl siloxane) copolymer was synthesized by a two-step process, initiated by coupling anhydride terminated poly(amic acid), AT-PAA with amino terminated poly(dimethyl siloxane), (NH2)2-PDMS to form poly(amic acid)-block-poly(dimethyl siloxane). The resulting copolymer is then thermally treated to produce polyimide-block-poly(dimethyl siloxane), PI-PDMS. Because of the high glass transition temperature, Tg of polyimide, it is usually cured at a high temperature of about 300°C for over 2.5 h. Copolymerization of polyimide with polysiloxane, reduces the imidization temperature while maintaining high thermomechanical properties. A series of instruments were used to monitor the progress of copolymerization. The time-based analysis of the product of copolymerization enables the optimization of the structure and properties of the copolymers. The chemical structure and composition of the copolymer were studied by Fourier Transform Infrared Spectroscopy, (FT-IR). The incorporation of PDMS blocks into the copolymer and the degree of imidization of the polyimide block increased with increasing reaction time. The change in the viscosity of the copolymerizing solution was monitored by simple shear viscometry conducted with the Brookfield Viscometer. The reported increase in solution viscosity with increasing copolymerization time is associated with increasing molecular weight of the copolymer. The intrinsic viscosity of the copolymer solution was measured as a function of copolymerization time and it was found that the intrinsic viscosity of the copolymer solution increased with increasing reaction time. The glass transition temperature (Tg) and the thermal stability of the copolymer were determined by differential scanning calorimetry, DSC and thermogravimetric analysis, and TGA, respectively. Between 25°C and 420°C, the copolymers synthesized in this study show two glass transition temperatures due to the polyimide, PI block at around 380°C and another peak associated with PDMS plasticized polyimide at about 290–300°C. The two Tg peaks observed in the DSC thermogram are believed to be indicative of the structure of a block copolymer. TGA analysis shows that the thermoxidative stability of the copolymers increased with increasing reaction time, due to the incorporation of increased amount of PDMS unit into the copolymer. The combination of increasing molecular weight of copolymer, higher degree of imidization of polyimide blocks and enhanced thermoxidative stability may translate into improved flame retardancy of copolymers. This suggested enhancement in flame retardancy in air atmosphere, is believed to be due the incorporated PDMS blocks, which can be converted into silica, SiO2, a recognized thermally stable material.