羰基和砜基共交联磺化聚酰亚胺质子交换膜的制备及燃料电池性能

为提高磺化聚酰亚胺质子交换膜(SPI PEM)的高温耐水解稳定性及电池性能,用3,5-双(4-氨基苯氧基)苯甲酸(BAPBa)制备了一系列六元环型SPI PEM,利用甲磺酸/五氧化二磷溶液(PPMA)制备了羰基和砜基共交联的SPI PEM.测定了SPI PEM的质子传导率、耐水解稳定性、机械性能及电池性能.结果表明,羰基和砜基共交联提高膜交联度的同时减少了磺酸基的消耗,使SPI PEM保持较高的质子传导率.在相对湿度为50%RH时,羰基和砜基共交联SPI PEM的质子传导率为7.8 m S/cm,比同样条件下砜基交联的SPI PEM提高28%.羰基和砜基共交联的SPI PEM在130℃水中老化500 h后断裂伸长率为18%,质子传导率未明显降低.羰基和砜基共交联SPI PEM作为电池时,最大功率密度达到0.85 W/cm2,是砜基交联PEM的1.3倍.     

Soluble and degradable polyimides with phenyl-2-pyridyl ether structure: Synthesis and characterization

A diamine monomer o-phenylenedioxybis(5-amino-2-pyridine) was synthesized via reduction of a dinitro compound o-phenylenedioxybis(5-nitro-2-pyridine), producing a series of new polyimides from this diamine and various commercially available aromatic dianhydrides via conventional two-stage processes. The resulting polyimides are able to form tough and transparent films, with decomposition temperatures in the range of 529–551 °C, and can be dissolved in organic polar solvents. Meanwhile, these polyimides can be degraded in a hydrazine hydrate medium, a degradation mechanism proposed by analyzing the degradation products suggests that the degradable properties could be attributed to the phenyl-2-pyridyl ether structure in the polymer. In addition, the transformation of the compound structure from dinitro compound to damine monomer in the synthetic process is discussed in respect to X-ray structure.     

Synthesis and characterization of high-barrier polyimide containing rigid planar moieties and amide groups

A high-performance polyimide was prepared by the dipolymerization of 4,4'-diaminobenzanilide (DABA) and pyromellitic dianhydride (PMDA). Due to the introduction of rigid planar moieties and amide groups, the polyimide shows outstanding properties, such as high glass transition temperatures (435 °C), excellent thermal stability (T_d5%, 542 °C, coefficient of thermal expansion, −3.2 ppm K⁻¹), and superior mechanical properties. Most importantly, the polyimide exhibits excellent barrier properties, with oxygen transmission rate (OTR) and water vapor transmission rate (WVTR) low to 7.9 cm³ (m² day)⁻¹ and 5.1 g (m² day)⁻¹, respectively. Wide angle X-ray diffractograms (WAXD), positron annihilation lifetime spectroscopy (PALS) and molecular dynamics simulations reveal that the excellent barrier properties are mainly attributed to the high crystallinity, high extent of in-plane crystalline orientation, and low free volume, which are resulted from the rigid planar structure and strong interchain hydrogen bonding. The high-barrier and thermally stable polyimide has an attractive potential application prospect in the fields of micro-electronics encapsulation and high grade packaging industry.     

Sequence‐Dependent Self‐Assembly of Chiral Polyimides

Sequence‐defined chiral polyimides comprising identical asymmetric diamine monomers arranged in different directions along the main chain were designed and prepared. These new sequence‐defined polymers exhibit sequence‐dependent self‐assembly behaviors and responses to ibuprofen enantiomers, as revealed by their chiroptical spectra and gelation properties. For the first time, the self‐assembly of polymers and their interactions with guest molecules have been successfully controlled by means of the directional arrangement of the monomers in their polymer backbones.     

Structure-property relationship study of partially aliphatic copolyimides for preparation of flexible and transparent polyimide films

The structure-property relationship of partially aliphatic copolyimides has been studied for the development of flexible, transparent polyimide films. A structurally rigid cycloaliphatic dianhydride and three aromatic dianhydrides having different structural flexibility were reacted with 4,4′-oxydianiline to prepare the copolyimides. In order to control the balance between aromaticity and aliphaticity and between rigidity and flexibility of the copolyimides, the molar ratio of the dianhydrides was varied. Polyimide properties such as viscosity, solubility, optical transparency, color, dielectric constants, film flexibility and thermal stability are influenced by aromaticity/aliphaticity and/or flexibility/rigidity of the monomers.     

Ultraviolet or Atomic Oxygen Effects on Tribological Properties of the Carbon Fibers/Polyimide Composites

Carbon fibers-reinforced polyimide composites (CF-PI) were fabricated by means of a hot press molding technique. To contrast the effects of ultraviolet and atomic oxygen irradiation under high vacuum on the tribological properties of CF-PI composites, the friction and wear properties of the composites sliding against GCr15 steel ball before and after irradiation were conducted in high vacuum on a ball-on-disk test rig. The experimental results revealed that CF-PI composites exhibited higher modulus and lower coefficient of friction and worn rate value than pure polyimide under high vacuum. However, the coefficient of friction of composites increased and the worn rate value decreased after ultraviolet or atomic oxygen irradiation, which slightly affected the tribological properties of CF-PI composites. The chemical composition of the composites changed after irradiation was inspected by X-ray photoelectron spectroscopy. Microstructure of the worn surfaces of the tested composites was investigated by scanning electron microscopy to reveal the wear mechanism.     

Effects of Aramid Fiber and Polytetrafluoroethylene on the Mechanical and Tribological Properties of Polyimide Composites in a Vacuum

Polyimide composites filled with aramid fiber (AF) and polytetrafluoroethylene (PTFE) were prepared by hot press molding. The thermal, mechanical, and tribological properties of the composites were studied systematically. The friction and wear behavior, sliding against GCr15 steel balls, were evaluated in a ground-based wear in space simulation facility using a ball-on-disk tribosystem. The morphologies of the worn surfaces during the sliding process of the composites were analyzed by scanning electron microscopy to reveal the wear mechanism. It was found that the heat-resisting performance and the hardness of the composites were minimally affected by the additives. The flexural strength of polyimide/AF/PTFE (PI-3) decreased when PTFE was added. The wear resistance increased and the coefficient of friction decreased due to the effect of both fillers. In vacuum, the friction coefficients of polyimide (PI-1), polyimide/AF (PI-2), and PI-3 increased slightly with sliding velocity, while the opposite results were obtained in air. With the increase of air pressure the friction coefficients of the samples increased.     

Effects of tetracarboxylic dianhydrides on the properties of sulfonated polyimides

A series of sulfonated polyimides (SPIs) were synthesized from a sulfonated diamine of 4,4′‐bis(4‐aminophenoxy) biphenyl‐3,3′‐disulfonic acid (BAPBDS), common nonsulfonated diamines, and various tetracarboxylic dianhydrides including 1,4,5,8‐naphthalene tetracarboxylic dianhydride (NTDA), 3,4,9,10‐perylene tetracarboxylic dianhydride (PTDA), 4,4′‐binaphthyl‐1,1′,8,8′‐tetracarboxylic dianhydride (BTDA), 4,4′‐ketone dinaphthalene 1,1′,8,8′‐tetracarboxylic dianhydride (KDNTDA), and isophthatic dinaphthalene 1,1′,8,8′‐tetracarboxylic dianhydride (IPNTDA). Their membrane properties were investigated to clarify the effects of the dianhydrides. They displayed reasonably high mechanical properties, thermal stability, and proton conductivity. The dianhydrides with flexible and non‐coplanar structure (IPNTDA > KDNTDA > BTDA) led to the better solubility of the SPIs than those with rigid and coplanar one (NTDA, PTDA). The dianhydride with the smaller molecular weight led to the larger value of the number of sorbed water molecules per sulfonic acid group (λ) in membrane, that is, NTDA (λ: 17) > PTDA (15) > BTDA (14) > KDNTDA (12) > IPNTDA (10), and as a result let to the larger proton conductivity in water. All of the BAPBDS‐based SPIs showed the anisotropy in membrane swelling and in proton conductivity, of which the degree hardly depended on the dianhydride moieties. The water stability of SPI membranes against the aging in water at 130 °C for 192 h was in the order, PTDA = NTDA ≧ BTDA > KDNTDA > IPNTDA. The hydrolysis stability of polymer chain was similar between the BTDA‐ and KDNTDA‐based SPIs. These results are discussed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 905–915, 2010     

Free radical initiated low temperature crosslinking of phenylethynyl (PE) end‐capped oligomides

A relatively low‐temperature crosslinking method for phenylethynyl (PE) end‐capped oligomides was developed. PE end‐capped oligomides are typically cured into crosslinked polyimides at 370 °C for about 1 h. The addition of a low viscosity mixed‐solvent of N‐methylpyrrolidinone (NMP)/dimethyl ether of polyethylene glycol (M = 250 g/mol), NMP/DM‐PEG‐250, or NMP/polyethylene glycol (M = 400 g/mol), NMP/PEG‐400, as film forming medium for PE‐end‐capped oligomides was investigated. Fourier transform infrared spectroscopy and ¹³C NMR showed that the mixed solvent addition was effective for achieving low‐temperature crosslinking of the ethynyl end‐caps over the temperature range 200–250 °C. The low temperature crosslinking process was explained by thermolysis of the PEG molecules over this temperature range forming free radical species such as ～CH₂CH₂O· or ～CH₂CH₂^· which initiate cure of the ethynyl groups resulting in a cross linked polyimide membrane. The PEG solvents also provide a radical source for the degradation polymerization of the solvents to a water and NMP insoluble polymer, which formed a miscible blend with the crosslinked membrane. Glass transition temperature (differential scanning calorimetry) data and thermo gravimetric analysis data provide evidence for the miscible blend. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3950–3963, 2010.     

Novel Poly(benzoxazole-etherimide) Copolymer for Two-Layer Flexible Copper-Clad Laminate

A new random co-polyimide (co-PI), poly(benzoxazole-etherimide), was prepared via the poly(amic acid) from the reaction of 5-amino-2-(4-aminobenzene)-1,3-benzoxazole (BOA) and 4,4′-oxydianiline (ODA) with 3,3′,4,4′-biphenyl tetracarboxylic dianhydride (BPDA) at a diamine molar ratio of 6:4. The BOA-type and ODA-type homo-PIs were also prepared for comparison. The aggregation structure and properties of the PI films were analyzed. The co-PI film showed a good balance in thermal properties, tensile strength, film toughness, and water absorption. The two-layer flexible copper-clad laminates made from these PIs were produced by coating poly(amic acid) solutions onto copper foils and then imidizing thermally. The adhesion properties and relative thermodimensional stability of the laminates were evaluated. The laminate based on the co-PI had higher relative thermodimensional stability as well as better adhesion property than those based on the two homo-PIs, which is due to the improvement in both the bonding strength of PI/copper at the interface and the cohesive strength of the co-PI itself in the boundary layer near the interface.