Chemistry of multifunctional polymers based on bis-MPA and their cutting-edge applications

Polymers play an important role in the advancement of materials for use in cutting-edge applications. A direct consequence of an increased demand for more sophisticated materials has been a drive toward developing polymers that exhibit a higher level of structural control, especially in terms of the number and type of functionalities provided within the polymer framework. A family of polymers that meets such a challenge is based on the readily available AB₂ monomer 2,2-bismethylolpropionic acid (bis-MPA) building block. Due to the ease with which the monomers can be synthesized, an array of multifunctional polymers have been produced including monodisperse dendrimers and dendrons and well-defined linear polymers as well as linear-dendritic hybridizations. This review outlines the evolution of the synthetic strategies for developing novel polymeric architectures based on bis-MPA and their assessment in both solution and substrate-based innovative applications.     

Facile modifications of polyimide via chloromethylation: II. Synthesis and characterization of thermocurable transparent polyimide having methylene acrylate side groups

From chloromethylated polyimide, a useful starting material for modification of aromatic polyimides, a thermocurable transparent polyimide having acrylate side groups was prepared. In the presence of 1,8‐diazabicyclo[5,4,0]undec‐7‐ene, chloromethylated polyimide was esterified with acrylic acid to synthesize poly(imide methylene acrylate). The polymer was soluble in organic solvent, which makes it possible to prepare a planar film by spin coating. The polymer film became insoluble after thermal treatment at 230 °C for 30 min. Optical transparency of the film at 400 nm (for 1 µm thickness) was higher than 98 % and not affected by further heating at 230 °C for 250 min. Adhesion properties measured by the ASTM D3359‐B method ranged from 4B to 5B. Preliminary results of planarization testing showed a high degree of planarization (DOP) value (>0.53). These properties demonstrate that poly(imide methylene acrylate) could be utilized as a thermocurable transparent material in fabricating display devices such as TFT‐LCD. Copyright © 2004 Society of Chemical Industry     

Time dependent crystal-smectic transformation in perylene-containing polyimides

The crystalline conformations of perylene polyimides (PPIs), with alkyl spacers varying in length from C₃ to C₁₂ are discussed. Although modeling of single chains would suggest the possibility that those with odd number of CH₂ groups adopt a flat helical shape, X-ray diffraction suggests that the chains with odd and even spacers have the same conformation, due to the necessity to pack the perylene units. Upon annealing, the UV-vis absorption maximum red-shifts by about 10 nm, indicating enhanced π-stacking between the perylenes. Several changes in the spectra are seen with an increase in annealing time, at a given temperature. With an increase in annealing time, X-ray diffraction patterns show changes in the number of reflections, indicative of a crystal to mesogenic transition. The time required for this transition increases with a decrease in the spacer length, and annealing temperature, suggesting that the dynamics of this transition is very slow.     

Organosoluble and light-colored fluorinated polyimides derived from 2,3-bis(4-amino-2-trifluoromethylphenoxy)naphthalene and aromatic dianhydrides

A novel fluorinated bis(ether amine) monomer, 2,3-bis(4-amino-2-trifluoromethylphenoxy)naphthalene, was prepared through the nucleophilic aromatic substitution reaction of 2-chloro-5-nitrobenzotrifluoride and 2,3-dihydroxynaphthalene in the presence of potassium carbonate, followed by catalytic reduction with hydrazine and Pd/C. A series of new fluorine-containing polyimides having inherent viscosities of 0.54 to 1.10 dl/g were synthesized from the diamine with various commercially available aromatic dianhydrides using a standard two-stage process with thermal imidization of poly(amic acid) films. These polyimides were highly soluble in a variety of organic solvents, and most of them afforded transparent, light-colored, and tough films with good tensile strengths. These polyimides exhibited glass transition temperatures (T_gs) of 247-300 °C and showed no significant decomposition below 500 °C under either nitrogen or air atmosphere. Except for the polyimide derived from pyromellitic dianhydride, the polyimide films were almost colorless, with an ultraviolet-visible absorption cutoff wavelength below 400 nm and low b∗ values (a yellowness index) of 10.7-41.9. These polyimides had dielectric constants of 3.09 to 3.65 (1 MHz) and moisture absorptions in the range of 0.2-0.3 wt%.     

Electrochemical behaviour of phenylethanolamine at gold in aqueous solution

The electrooxidation of phenylethanolamine (2-amino-1-phenylethanol) at a gold electrode in alkaline electrolyte has been studied. Measurement of the differential capacitance of the electric double layer versus the electrode potential has shown that the adsorption of phenylethanolamine at the gold-solution interface plays a significant role in the oxidation mechanism. The effect of amine concentration, electrolyte pH and potential scan rate on the electrooxidation is analysed.     

High-temperature polyimide nanofoams for microelectronic applications

Foamed polyimides have been developed in order to obtain thin film dielectric layers with very low dielectric constants for use in microelectronic devices. In these systems the pore sizes are in the nanometer range, thus, the term ‘nanofoam’. The polyimide foams are prepared from block copolymers consisting of thermally stable and thermally labile blocks, the latter being the dispersed phase. Foam formation is effected by thermolysis of the thermally labile block, leaving pores of the size and shape corresponding to the initial copolymer morphology. Nanofoams prepared from a number of polyimides as matrix materials were investigated as well as from a number of thermally labile polymers. The foams were characterized by a variety of experiments including TEM, SAXS, WAXD, DMTA, density measurements, refractive index measurements and dielectric constant measurements. Thin film foams, with high thermal stability and low dielectric constants approaching 2.0, can be prepared using the copolymer/nanofoam approach.     

Carbon fibre composites based on polyimide/silica ceramers: aspects of structure-properties relationship

Polyimide/silica ceramers, based on the products of the hydrolysis of tetraethoxysilane (TEOS) and a commercial poly(amic acid) solution, were used to fabricate unidirectional carbon fibre composites, which were subsequently evaluated with respect to thermal and mechanical properties. There is evidence to suggest that the silica component of these ceramers is present as dispersed discrete particles at low silica concentration (i.e. 7 wt%) and as fine interconnected domains trapped within the polyimide matrix at higher silica content (i.e. 14 wt%). The dimensions of the silica domains were in the region of 7–20 nm. Carbon fibre composites produced from ceramer solutions (CF/ceramers) were found to exhibit lower thermal expansion and a greater retention of flexural and interlaminar shear properties at elevated temperature than the corresponding polyimide-matrix composites (CF/polyimide). The properties of CF/ceramers were generally better for systems containing the higher amount of silica and were improved further by lowering the pH value of the precursor ceramer solution. This is believed to have resulted from the enhanced fluidity of the ceramer gel within the pre-impregnated fibres, giving rise to a higher packing density of the fibres and a more homogeneous distribution of fibres. CF/ceramers were also found to exhibit a better thermal oxidative stability at 350°C than the corresponding CF/polyimide, although a substantial amount of porosity developed in the case of ceramers with the higher silica content.     

Low Dielectric Polyimide/Fluorinated Ethylene Propylene (PI/FEP) Nanocomposite Film for High-Frequency Flexible Circuit Board Application

The low dielectric polymer films have drawn great attention to the application as the dielectric insulating materials in high-frequency circuit boards, while the weak adhesion to the copper foils and the poor processability resulted from the fluorinated or rigid structures limited their high-frequency application. In this work, the low dielectric and high adhesive polyimide/fluorinated ethylene propylene (PI/FEP) nanocomposite film for high-frequency flexible circuit board application is developed. It is indicated that the fluorocarbon surfactants can significantly improve the dispersion of FEP in PI substrate, and thus, the PI/FEP nanocomposite film exhibits excellent mechanical properties, including the tensile strength increases to 46.6 MPa and the elongation at the break increases to 13.7%. Importantly, at the high-frequency of 10 GHz, the 60 wt% FEP filled PI nanocomposite film displays an ultralow dielectric loss (0.006) and a reduced dielectric constant (2.69). In addition, the high-frequency flexible circuit board with the PI/FEP film as the dielectric insulating layer has a high peel strength of 0.75 N mm⁻¹, indicating this PI/FEP nanocomposite film can meet the requirements of the high-frequency flexible circuit board application.     

Excellent Polyimide Dielectrics Containing Conjugated ACAT for High-Temperature Polymer Film Capacitor

In order to meet the requirements of polymer dielectric materials for high thermal stability and excellent dielectric properties in the application of high-temperature film capacitors, a series of polyimide (PI) films are fabricated by introducing a self-synthesized aniline trimer (ACAT) with a conjugated structure in this work. Since the conjugated ACAT in the main chains of PI improves the electron polarization and carrier mobility of the PI molecular chains, the dielectric constant of the ACAT-PI films is greatly enhanced (4.4–7.4). Meanwhile, the dissipation factor does not increase apparently (0.002–0.013). The dielectric properties are stable even when the temperature is up to 200 °C, the thermal degradation temperature is as high as 450 °C, and the mechanical properties are also excellent (70–105 MPa). Among all the films, the PI film with 5 mol% ACAT exhibits the maximal energy density of 3.6 J cm⁻³ under the field of 426 kV mm⁻¹, the high tensile strength (90 MPa) and the excellent thermal stability (T_d5 = 515 °C). The work paves the way to prepare high-temperature polymer dielectric film materials with high energy storage density.     

Synthesis and characterization of aromatic polyisoimides derived from PMDA and para-diamines. An approach to in situ generated rigid-rod molecular composites

A new concept for the processing and fabrication of rigid-rod molecular composites aiming at the elimination or minimization of phase separation is proposed. This approach calls for a coil-like aromatic polyisoimide which is soluble and compatible with an amorphous matrix polymer or thermosettable oligomer and can undergo facile transformation to the corresponding rigid-rod polyimide in solid composite state, thus imparting the inherently high strength/high modulus properties to the final form. To this end, various synthetic routes were explored to obtain para-diamines which could afford high molecular weight and aprotic-solvent-soluble polyisoimides upon polymerization with pyromellitic dianhydride (PMDA). Four such polyisoimides were prepared, with their inherent viscosities ranging from 0.25 to 1.89 dl g⁻¹ in dimethylacetamide at 30°C. Facile thermally induced isoimide-imide conversion was demonstrated by solid-state (film) Fourier transform infrared spectroscopy. A preliminary evaluation of the compatibility of the polyisoimide/matrix resin was made. In one instance, a film prepared from the polyisoimide derived from PMDA and 3,3′,5,5′-tetramethylbenzidine (TMB) showed no visually detectable phase separation.