Synergistic improvement of mechanical and thermal properties in epoxy composites via polyimide microspheres

Achieving synergetic improvements of mechanical strength, toughness, and thermal stability of epoxy resin has been a crucial but very challenging issue. Herein, to explore a new solution for circumventing this issue, polyimide microspheres were successfully prepared through the inverse nonaqueous emulsion process, and the structure, size distribution and morphologies of polyimide (PI) microspheres were comprehensively investigated. Then the PI microspheres were incorporated in epoxy resin matrix to systematically investigate the mechanical and thermal properties of obtained epoxy/PI microspheres composites. It was found that the PI microspheres can not only enhance the mechanical strength of epoxy resin, but also significantly improve the toughness. Specially, the epoxy-based composites containing 3 wt% PI microspheres exhibit a 47% increase in tensile strength, while the G_IC and Charpy impact strength increase by 106% and 200%, respectively. The toughing mechanism of epoxy/PI microspheres composites was discussed. Moreover, the PI microspheres can also endow the epoxy resin with excellent thermal stability and heat resistance. Thus, this work may open a new opportunity to synergistically enhance the mechanical and thermal properties of epoxy-based composites and may also give some valuable inspiration for the rational design of other high-performance thermosetting composites.     

Synthesis and thermal,mechanical and gas permeation properties of aromatic polyimides containing different linkage groups

Two series of aromatic polyimides containing various linkage groups based on 2,7‐bis(4‐aminophenoxy)naphthalene or 3,3′‐dimethyl‐4,4′‐diaminodiphenylmethane and different aromatic dianhydrides, namely 4,4′‐(4,4′‐isopropylidenediphenoxy)bis(phthalic anhydride), 4,4′‐(hexafluoroisopropylidene)bis(phthalic anhydride), 3,3′,4,4′ benzophenonetetracarboxylic dianhydride, 9,9‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]fluorene dianhydride and 4,4′‐(4,4′‐hexafluoroisopropylidenediphenoxy)bis(phthalic anhydride), were synthesized and compared with regard to their thermal, mechanical and gas permeation properties. All these polymers showed high thermal stability with initial decomposition temperature in the range 475–525 °C and glass transition temperature between 208 and 286 °C. Also, the polymer films presented good mechanical characteristics with tensile strength in the range 60–91 MPa and storage modulus in the range 1700–2375 MPa. The macromolecular chain packing induced by dianhydride and diamine segments was investigated by examining gas permeation through the polymer films. The relationships between chain mobility and interchain distance and the obtained values for gas permeability are discussed. © 2014 Society of Chemical Industry     

Equilibrium,kinetics, and thermodynamics of Pd(II) adsorption onto poly(m‐aminobenzoic acid) chelating polymer

This study describes the equilibrium, kinetics, and thermodynamics of the palladium(II) (Pd(II)) adsorption onto poly(m‐aminobenzoic acid) (p‐mABA) chelating polymer. The p‐mABA was synthesized by the oxidation reaction of m‐aminobenzoic acid monomer with ammonium peroxydisulfate (APS). The synthesized p‐mABA chelating polymer was characterized by FTIR spectroscopy, gel permeation chromatography (GPC), thermal analysis, potentiometric titration, and scanning electron microscopy (SEM) analysis methods. The effects of the acidity, temperature, and initial Pd(II) concentration on the adsorption were examined by using batch adsorption technique. The optimum acidity for the Pd(II) adsorption was determined as pH 2. In the equilibrium studies, it was found that the Pd(II) adsorption capacity of the polymer was to be 24.21 mg/g and the adsorption data fitted better to the Langmuir isotherm than the Freundlich isotherm. The kinetics of the adsorption fitted to pseudo‐second‐order kinetic model. In the thermodynamic evaluation of the adsorption, the ΔG° values were calculated as ?16.98 and ?22.26 kJ/mol at 25–55°C temperatures. The enthalpy (ΔH°), entropy (ΔS°), and the activation energy (E_a) were found as 35.40 kJ/mol, 176.05 J/mol K, and 61.71 kJ/mol, respectively. The adsorption of Pd(II) ions onto p‐mABA was a spontaneous, endothermic, and chemical adsorption process which is governed by both ionic interaction and chelating mechanisms. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42533.     

Effect of the microscopic morphology of a filler on its dispersion in a PI matrix: Calculation and analysis

The preparation of crosslinked polyimide (PI) composites via a blending technique is reported. Different kinds of organic or inorganic silicon-based nanofillers have been used for this purpose. A comparison is made between carefully chosen pairs of fillers, the choice depending on the compatibility of the crosslinked PI with the filler, to study the effects of the crosslinked PI matrix structure and fillers with different micromorphology. The dispersion of the filler is characterized with SEM as uniformly dispersed or gelled. It is found that with different micromorphology of filler, the PI matrix can be loaded with different mass fractions of filler, and the point at which gelation occurs is not the same. In order to study this behavior, these fillers are subjected to a quadratic mean equation calculation and analysis. Compared to pure PI, all obtained crosslinked composites have a higher glass-transition temperature and a lower dielectric constant. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46875.     

Colorless polyimides with low coefficient of thermal expansion derived from alkyl‐substituted cyclobutanetetracarboxylic dianhydrides

Alkyl‐substituted cyclobutanetetracarboxylic dianhydrides (CBDAs) were synthesized by photo‐dimerization of alkyl‐substituted maleic anhydrides to obtain novel colorless polyimides (PIs). Dimethyl‐substituted CBDA (DM‐CBDA) showed much higher polymerizability with various diamines than conventional cycloaliphatic tetracarboxylic dianhydrides and led to high molecular weights of PI precursors. Polyaddition of non‐substituted CBDA and trans‐1,4‐cyclohexanediamine (t‐CHDA) was completely inhibited by salt formation in the initial reaction stage. The use of DM‐CBDA allowed the formation of a homogeneous/viscous PI precursor solution by overcoming the salt formation problem. The prominent substituent effect probably reflects how the methyl substituents of DM‐CBDA contributed to increasing the salt solubility. Some of the thermally imidized DM‐CBDA‐based systems simultaneously possessed non‐coloration, low coefficient of thermal expansion (CTE), very high T_g exceeding 300 °C and very low dielectric constant. Copolymerization was very effective for improving the solubility of DM‐CBDA‐based PIs. The copolyimide cast films prepared via chemical imidization displayed a further decreased CTE without sacrificing other target properties, suggesting that the present materials can be useful as plastic substrates in display devices. The mechanism of self‐chain orientation behavior during solution casting is also discussed. A potential application of the copolyimide systems as optical compensation film materials in liquid crystal displays is proposed. © 2013 Society of Chemical Industry .     

Imide‐containing ladder polyphenylsilsesquioxanes with high thermal stability and thermoplastic properties

This work reports for the first time the synthesis of ladder polyphenylsilsesquioxanes containing imide building blocks as parts of the main parallel chains. The ladder structure of the synthesized polymers was documented by means of small angle X‐ray scattering (SAXS) measurements. The obtained ladder polymers exhibit stability with respect to decomposition up to temperatures as high as 460°C; additionally, they have melting points far below their decomposition temperatures, which make them interesting candidate materials for thermoplastic processing. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40085.     

Synthesis and properties of organosoluble polyimides based on 1,1-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]cyclohexane

New aromatic diamine with cyclohexane cardo group substituted with trifluoromethyl group in the side chain, 1,1-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]cyclohexane (II), was prepared through the nucleophilic substitution reaction of 1,1-bis(4-hydroxyphenyl)cyclohexane and 2-chloro-5-nitrobenzotrifluoride in the presence of potassium carbonate, to yield the intermediate dinitro compound I, followed by catalytic reduction with hydrazine and Pd/C to afford the diamine II. Fluorinated polyimides (IVa-g) were prepared from the II with various aromatic dianhydrides via thermal or chemical imidization of poly(amic acid). These polyimides had inherent viscosity ranging from 0.72 to 1.16 dl/g and showed excellent solubility in a variety of organic solvents. They were soluble in a concentration of 10% in the amide polar solvent, and 1-5% in the other testing solvents. IV films showed good mechanical properties, excellent thermal stability. The 10% weight loss temperature was above 476 °C in nitrogen or air, and the glass transition temperature was recorded at 214-278 °C. In comparison of the IV series with the analogous nonfluorinated polyimides (V series) based on 1,1-bis[4-(4-aminophenoxy)phenyl]cyclohexane (II′), IV series revealed better solubility, lighter-colored and lower dielectric constants and moisture absorptions. Their films had cut-off wavelengths in the range of 364-414 nm, b^* value (a yellowness index) ranging from 3.3 to 66.3, dielectric constants of 3.02-3.55 (1 MHz), with moisture absorption of 0.16-0.36 wt%.     

Preparation and properties of (BATB–ODPA) polyimide–clay nanocomposite materials

A series of polymer–clay nanocomposite (PCN) materials consisting of 1,4‐bis(4‐aminophenoxy)‐2‐tert‐butylbenzene–4,4′‐oxydiphthalic anhydride (BATB–ODPA) polyimide (PI) and layered montmorillonite (MMT) clay were successfully prepared by an in situ polymerization reaction through thermal imidization up to 300°C. The synthesized PCN materials were subsequently characterized by Fourier‐Transform infrared (FTIR) spectroscopy, wide‐angle powder X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The effects of material composition on thermal stability, mechanical strength, molecular permeability and optical clarity of bulk PI and PCN materials in the form of membranes were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), molecular permeability analysis (GPA) and ultraviolet‐visible (UV/VIS) transmission spectra, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1072–1079, 2004     

Synthesis and properties of polyimides derived from cis- and trans-1,2,3,4-cyclohexanetetracarboxylic dianhydrides

Cis-1,2,3,4-cyclohexanetetracarboxylic dianhydride (cis-1,2,3,4-CHDA) was synthesized. It was found that under such conditions as heating or boiling in acetic anhydride, cis-1,2,3,4-CHDA could be converted to its trans-isomer. The process of thermal isomerization was monitored by ¹H NMR spectra and the mechanism of conversion was proposed. Their absolute structures of cis- and trans-1,2,3,4-CHDAs were elucidated by single crystal X-ray diffraction. The polycondensations of cis- and trans-1,2,3,4-CHDAs with aromatic diamines such as 4,4′-oxydianiline (ODA), 4,4′-methylenedianiline (MDA), 4,4′-diamino-3,3′-dimethyldiphenylmethane (DMMDA), 4,4′-bis(4-aminophenoxy)benzene (TPEQ), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) were studied. It is easy to obtain higher molecular weight polyimides from trans-1,2,3,4-CHDA using conventional one-step or two-step methods. However, higher molecular weight polyimides derived from cis-1,2,3,4-CHDA could not be prepared by the usual methods (solid content ca. 10%) owing to the trend of forming cyclic oligomers. Increasing the concentration of monomers could give higher molecular weight cis-polymers. All of the cis-polyimides were soluble at room temperature in aprotic polar solvents and phenolic solvents and some of them even soluble in chloroform and tetrahydrofuran, while the corresponding trans-polymers showed poor solubility as compared to cis-polymers. All of the polyimides showed good thermal stability with the 5% weight loss temperatures in air over 415 °C. Furthermore, polyimides derived from cis-1,2,3,4-CHDA have higher glass transition temperatures (T_gs) than corresponding trans-polyimides. The flexible polyimide films possessed a tensile modulus range of 2.1-3.6 GPa, a tensile strength range of 42-116 MPa, an elongation at break of 4-18%. These polyimides exhibited cutoffs at wavelengths around 270 nm and were entirely colorless. All the polyimides showed amorphous pattern according to Wide angle X-ray diffraction measurements. The differences of polymerization and properties were explained by the structural changes resulted from isomerism.