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.     

Graphene oxide-containing isocyanate-based polyimide foams: Enhanced thermal stability and flame retardancy

Isocyanate-based graphene oxide-containing polyimide foams were synthesized by a semi-prepolymer method. In this method, while the first solution containing pre-polymer was derived from pyromellitic dianhydride and excess polymethylene polyphenylene isocyanate (PM200), the second solution contains dianhydride derivatives, water, catalysts, surfactants, and graphene oxide. PIFs were prepared with 0%, 0.25%, 0.50%, 0.75%, and 1% graphene oxide by weight, respectively. PIFs exhibited a minimum side reaction and urea generation was not seen for all PIFs instead of imide bonding. The addition of graphene oxide (GO) leads to a more close-packed structure. Therefore, crosslinking density and thermal stability of graphene oxide-containing polyimide foams increased. Upon the addition of 1% GO, almost seven times higher compression strength was obtained compared to neat PIFs. Also, LOI values supported the theory that thermally stable and flame retardant PIFs can be synthesized via the isocyanate-based process with GO.     

Letter: Solution‐processed flexible zinc‐tin oxide thin‐film transistors on ultra‐thin polyimide substrates

In this letter, solution‐processed flexible zinc‐tin oxide (Z_0.35T_0.65O_1.7) thin‐film transistors with electrochemically oxidized gate insulators (AlOx:Nd) fabricated on ultra‐thin (30 µm) polyimide substrates are presented. The AlOx:Nd insulators exhibited wonderful stability under bending and excellent insulating properties with low leakage current, high dielectric constant, and high breakdown field. The device exhibited a mobility of 3.9 cm²/V · s after annealing at 300 °C. In addition, the flexible device was able to maintain the electricity performance under various degrees of bending, which was attributed to the ultra‐thin polyimide substrate.     

双胺芴基聚酰亚胺的合成及性能

以9,9-双(4-氨基苯基)芴(BAF)为二胺,分别与6种二酐单体——均苯四甲酸二酐(PMDA)、3,3’,4,4’-二苯醚四甲酸二酐(ODPA)、3,3’,4,4’-二苯甲酮四甲酸酐(BTDA)、3,3’,4,4’-联苯四甲酸二酐(BPDA)、4,4'-(六氟异丙烯)二酞酸酐(6FDA)和1,2,3,4-环丁烷四甲酸二酐(CBDA),经室温溶液缩聚反应得到聚酰胺酸溶液,再经化学酰亚胺化反应得到芴基聚酰亚胺(PI)。采用红外光谱、差示扫描量热分析、热重分析、溶解性测试及气体分离性能测试等手段对PI的结构和性能进行了表征。所合成的PI在N-甲基吡咯烷酮(NMP)等强极性溶剂中均具有良好的溶解性,且表现出良好的热性能,玻璃化转变温度(Tg)均在300℃以上,芳香族PI的起始热分解温度也均超过500℃,经600℃热处理的芴基PI,表现出了较好的气体渗透性能,但PI-CBDA膜的气体通量最小。     

Branched aliphatic polyesters by ring-opening (co)polymerization

The rapid development of biodegradable and biocompatible materials for biomedical applications is reflected in the search for new methods for aliphatic polyester modification applicable in this field. One possible approach is modification by changes to the polymer topology.This review covers the main methods of synthesis of branched aliphatic biodegradable and biocompatible (co)polyesters, where the ring-opening polymerization (ROP) of cyclic esters or cyclic carbonates is the leading process. First, literature examples of ring-opening multibranching polymerization (ROMBP) of AB₂-type hydroxyl-substituted cyclic lactones, lactides and carbonates are cited followed by the presentation of the application of AB-type cyclic esters and additionally AB₂ cyclic ethers or esters as “branching monomers” for the synthesis of branched polyesters based on polycaprolactone (PCL), polylactide (PLA) and polyglycolide (PGA). In the following part, methods involving the combination of the ROP of AB-type cyclic esters and condensation processes leading to branched structures are summarized. Other related strategies leading to “dendri-star” or “core–shell” copolyesters are also discussed. Several examples of approaches to PCL and PLA graft copolymer syntheses are also shown. The advantages and disadvantages of the presented methodologies of branched polyester synthesis are highlighted. Finally, the influence of the branched structure on the properties of the presented class of polyesters, important from the application point of view, is considered.     

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 .     

Synthesis and characterization of novel polyimides containing triazoles units in the main chain by click chemistry

In this study, some polyimides containing triazoles units in the main chain was prepared from the polymerization of dialkynes including imide linkages and diazides in the presence of Cu (I) catalyst in yield of 76.2–87.6%, with inherent viscosity of 0.37–0.53 dL g^?1. The obtained polymers are soluble in polar aprotic solvents such as N,N‐dimethyformamide (DMF), N,N‐dimethyacetamide (DMAc), dimethyl sulfoxide (DMSO), and N‐methyl‐2‐pyrrolidone (NMP). These polymers were characterized using FT‐IR, ¹H‐NMR, and elemental analysis techniques. Their thermal stability was evaluated with thermogravimetric (TGA) analysis and differential scanning calorimetry (DSC) techniques under a nitrogen atmosphere which is indicative of their good thermal stability. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Mild oxidative degradation of spent auricularia auricular substrate and molecular composition of carboxylic acids in the resulting soluble portion

Spent auricularia auricular substrate(SAAS) was oxidatively degraded with aqueous hydrogen peroxide(AHPO)/acetic anhydride(AAH) to produce carboxylic acids(CAs) under mild conditions. The results show that up to 53.6% of the organic matter in SAAS was converted to the soluble species(SSs). In total 122 CAs were detected in the SSs by the analysis with a gas chromatograph/mass spectrometer, which can be classified into 29 group components, mainly being aliphatic acids and along with small amount of aromatic acids. Among the aliphatic acids, normal alkanedioic acids are the most abundant. The detected aromatic acids include benzoic acids,phthalic acids, trimellitic acids, pyromellitic acids, and their derivatives. The synergistic oxidation and the released ·OH, CH_3COO·, and HOO· induced by AHPO/AAH play crucial roles in oxidatively degrading SAAS.     

Effect of fluorination on haze reduction in transparent polyimide films for flexible substrates

High transmittance is an important parameter for polyimide (PI) films used as flexible display substrates. However, thermal treatment during film fabrication can cause an undesired phenomenon affecting color change in the films, which is called haze. Until now, haze formation in PI films has remained mostly unexplored, suggesting that originates in the composition. In this work, the effect of fluorination on haze reduction was investigated. Both experiments and density functional theory calculations suggest that a high degree of fluorination of PI repeating units results in weaker intra/intermolecular conjugations between polymer chains and higher haze resistance in the following order: one fluorinated group (−1.43 eV) > two fluorinated groups (−0.76 eV) > three fluorinated groups (−0.52 eV) > four fluorinated groups (−0.43 eV). The differences in the haze resistance can influence on haziness in the PI films by thermal gradient inside a lab scale cavity in a furnace. The obtained results indicate that slow heat transfer facilitates the manufacturing process to obtain high transparency in PI films. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44375.     

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.