Surface properties and antibacterial testing of a partially alicyclic polyimide film modified by RF plasma and NaOH/AgNO3 treatment

A polyimide containing alicyclic sequences was synthesized by a two steps solution polycondensation reaction and further processed into the film form for antibacterial purposes. The sample surface was activated by RF plasma treatment to ensure the biocide attachment by immersion in by NaOH/AgNO₃ solution. Surface properties of the synthesized polyimide film were analyzed by FTIR, contact angle and atomic force microscopy measurements, before and after the treatments with plasma and silver-based biocide. Antibacterial tests revealed that the pristine sample inhibit the growth of Staphylococcus aureus ATCC 25923 and Escherichia coli ATCC 25922, and this behavior is more pronounced after the biocide surface treatment. The differences in the biocidal activity were discussed in terms of sample and bacteria hydrophobic/hydrophilic interactions.     

含酰胺结构超低膨胀聚酰亚胺薄膜的热膨胀行为

采用联苯二酐与3种含酰胺结构二胺制备了具有不同取代基团的聚酰胺-酰亚胺薄膜, 考察了酰胺结构对薄膜力学、 耐热及尺寸稳定性的影响, 研究了聚集态结构与薄膜热膨胀行为的关系和规律. 该系列薄膜具有超高强度和优异的耐热性能, 拉伸强度高达280.5 MPa, 玻璃化转变温度在389~409 ℃, 并在30~300 ℃温度范围内表现出超低负膨胀, 热膨胀系数(CTE, ppm/℃, 即10 ⁶ cm·cm ^-1·℃ ^-1)在-3.05~-1.74 ppm/℃之间. 聚集态分析结果表明, 酰胺结构使分子链间形成了强氢键相互作用, 分子链在薄膜面内方向高度有序取向, 并在膜厚方向堆积更为紧密, 使薄膜表现出热收缩现象. 通过不同体积大小的取代基团进一步调控分子链间相互作用及排列堆积, 可实现薄膜在高温下近乎零尺寸形变, 为设计制备超低膨胀聚合物基板材料提供了新思路.     

Insights into MWCNTs/polyimide nanocomposites: from synthesis to application as free-standing flexible electrodes in low-cost micro-supercapacitors

In the pursuit to enlarge the library of polyimide materials for energy applications, new polyimide/MWCNTs composite films have been developed by MWCNTs-assisted polycondensation reaction of a hydroxyl and triphenylmethane-containing diamine with benzophenone tetracarboxylic dianhydride targeting to highlight their electrical storage capability as flexible electrodes in micro-supercapacitors (mSCs). The Fourier-transform infrared spectroscopy, proton nuclear magnetic resonance, UV–vis, fluorescence, and Raman spectroscopies were used to demonstrate the evolution of interfacial interactions between MWCNTs and the precursors (diamine monomer and intermediate polyamidic acid) and polyimide matrix that proved to be the origin of MWCNTs homogeneous dispersion. Thus, composite films incorporating 1, 3, 5, and 10 w.t.% MWCNTs were obtained and thoroughly investigated with regard to their morphology, mechanical behavior, thermal stability, and electrical conductivity. The electrochemical performance of these composites was first analyzed in a classical three-electrode cell by cyclic voltammetry and galvanostatic charge-discharge in both aqueous and organic electrolyte systems. By far, the best electrical storage capacity was obtained with the composite polyimide film containing 10% MWCNTs that was further used as both active material and current collector in a flexible symmetric mSC realized by a straightforward and low-cost procedure. In the attempt to better exploit the advantages of this composite film, it was layered with a graphite-containing paint and tested as an electrode in a flexible mSC, which provided satisfactory results. To our knowledge, this is the first report on the electrical charge storage capability of a polyimide/MWCNTs free-standing film as a flexible electrode in mSCs, which do not require time- and resource-consuming processing steps.     

Catalysis and inhibition of benzimidazole units on thermal imidization of poly(amic acid) via hydrogen bonding interactions

The effect of benzimidazole units on thermal imidizaiton was studied when they were introduced into the main chain of poly(amic acid)(PAA). The thermal imidization process of PAA-PABZ synthesized by 3,3',4,4'-biphenyltetracarboxylic dianhydride(BPDA) and 2-(4-aminophenyl)-5(6)-aminobenzimidazole(PABZ) was studied by TGA, DSC, DMA, FTIR and in situ FTIR. The results of FTIR and in situ FTIR indicate benzimidazole units act as an "in situ" catalyst to accelerate thermal imidization of PAA to polyimide(PI) when the temperature is lower than 170 °C. FTIR and 1H-NMR results demonstrate that in situ catalysis is caused by the hydrogen bonding interactions between C=N of benzimidazole and ―NH― in ―CONH― of PAA and the semi-ionization of the H in imidazole ring of benzimidazole. However, when the imidization temperature is higher than 170 °C, the thermal imidization process is inhibited. DMA and in situ FTIR results illustrate that the decreased mobility of PI-PABZ macromolecular chains and the reduced reactive ability of anhydride formed during the intramolecular breakdown of polymer chains lead to the inhibition of thermal imidization process.     

CO_2捕集炭膜的前驱体结构设计及性能

从分子结构设计出发,合成了一系列新型刚性、高自由体积的聚酰亚胺炭膜前驱体,并制备了炭膜.采用热重分析(TGA)、傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)和高分辨透射电子显微镜(HRTEM)研究了不同聚酰亚胺前驱体的热分解特性及在热解炭化过程中化学结构、微结构的变化规律;测试了所制备炭膜的气体分离性能.结果表明,前驱体的自由体积分数显著影响炭膜的气体分离性能;聚合物结构越具刚性,自由体积越大,所得炭膜结构越疏松,极微孔道尺寸越大,越有利于气体分子在炭膜极微孔道中的渗透、扩散与传输.其中,刚性大体积基团芴基、酚酞cardo基团和六氟异丙基的引入能有效破坏分子链间的堆积,提高聚合物的自由体积,所形成炭膜的结构较疏松,均表现出优异的气体渗透性和分离选择性,超越了Robeson上限,解决了传统炭膜气体渗透性能低的问题.特别是采用羟基官能化聚酰亚胺前驱体制备的炭膜在保持较高气体分离选择性的同时,CO_2气体的渗透性高达24770 Barrer(1 Barrer≈7.5×10-18m2·s-1·Pa-1),可实现对CO_2的有效分离和捕集,展现出良好的商业化应用前景.     

基于乙炔基-苯并噁嗪单元双重交联反应的聚酰亚胺树脂的制备与性能

为开发可低温固化的聚酰亚胺树脂, 通过分子结构设计将苯并噁嗪单元引入聚酰亚胺树脂中, 合成了含苯并噁嗪单元及乙炔基封端的双官能化新型聚酰亚胺预聚体(PIBzA). 经高温处理, 苯并噁嗪单元发生开环交联, 同时, 乙炔基端基发生三聚成环反应, 从而在固化树脂中形成双重交联网络结构. 苯并噁嗪单元的引入使聚酰亚胺树脂最快固化反应温度降低约32 ℃, 有效降低了固化温度. 同时, 苯并噁嗪单元的引入未大幅度降低树脂的耐热稳定性, 其玻璃化转变温度(T_g)介于266~290 ℃之间, 5%热失重温度(T_d,5%)接近500 ℃, 依然可以满足耐高温复合材料的应用需求. 此外, PIBzA固化树脂具有低介电特性, 其介电常数k介于2.3~3.0, 介电损耗介于0.002~0.008, 可满足透波复合材料及先进微电子封装材料的应用需求.     

Preparation of Low-dielectric Permittivity Polyimide Resins with High Surface Activity from Chemically Bonded Hyperbranched Polysiloxane

Thermosetting resin matrix is the key component of advanced wave-transparent composites,where low dielectric constant,excellent processability,high thermal stability,as well as good bonding ability are required for resins.Herein,we prepared a series of phenylethynyl terminated polyimide(PI)resins by grafting amine-functionalized hyperbranched polysiloxane(HBPSi)to PI chains during the in situ polymerization.The effects of HBPSi on the processability of oligomers,molecular packing,thermal stability,dielectric property and bonding ability to reinforce Kevlar fibers of the cured PI/HBPSi composite resins have been examined in detail.The dielectric constants of the cured composite resins were greatly reduced from 3.29 to 2.19 without compromising its processability and thermal stability.Meanwhile,the 10 wt％HBPSi-containing PI resin demonstrated better bonding ability to reinforce fibers with the interfacial shear strength(IFSS)of 37.64 MPa,compared with that of neat PI-6 matrix(27.34 MPa),and better adhesion to metal with the lap shear strength of 10.48 MPa,50％higher than that of neat resin PI-6(6.98 MPa).These resultant PI/HBPSi composite resins exhibit excellent comprehensive properties,indicating their great potential as low-dielectric constant resin matrix in radar radome.     

Polylactones. 13. Transesterification of Poly(L-Lactide) with Poly(Glycoude), Poly(β-Propio-Lactone), and Poly[ε -Caprolactone)

Homogeneous blends of poly(L-lactide) (M _n = 30 000 to 40 000) and poly(β-propiolactone) or poly(ε-caprolactone) were prepared in solution. The solvent-free blends were subjected to transesterification catalyzed by means of methyl triflate, triflic acid, boron trifluoride, or tributyltin methoxide at 100 or 150°C. At 100°C, transesterification was barely detectable even after 96 h. When poly(β-propiolactone) was used as the reactant at 150°C, degradation was faster than transesterification regardless of the catalyst. The same negative result was obtained for heterogeneous blends of poly(L-lactide) and poly(glycolide). In the case of poly(ε-caprolactone), copolyesters with slightly blocky sequences were obtained with tributyltin methoxide as catalyst, whereas the acidic catalysts caused rapid degradation. The copolyesters were characterized by means of ¹H-NMR spectroscopy with regard to their molar composition, by means of ¹³C-NMR spectroscopy with regard to their sequences, and by means of differential scanning calorimetry with regard to crystallinity.     

Inducing a high twisted conformation in the polyimide structure by bulky donor moieties for the development of non-volatile memory

Two polyimides, PI(DAT-6FDA) and PI(DAPT-6FDA), from N-(2,4-diaminophenyl)-N,N-diphenylamine (DAT) or N-(4-(2′,4′-diaminophenoxy)phenyl-N,N-diphenylamine (DAPT) and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) were prepared to clarify the structural effect on the resulting memory properties. The memory device based on PI(DAT-6FDA) showed an unstable volatile behavior, while the device based on PI(DAPT-6FDA) with a more bulky donor (D) unit exhibited a stable non-volatile FLASH type memory characteristic with a long retention time over 10⁴ s. The theoretical simulation based on the density functional theory (DFT) suggested that the greater distinct charge separation between the ground and charge transfer (CT) states led to a highly stable memory behavior. Also, it was clarified that PI(DAPT-6FDA) had a highly twisted conformation compared to PI(DAT-6FDA) in the ground state, and a more twisted dihedral angle between the D and acceptor (A) units was induced in the CT state, which led to the non-volatile memory characteristic.     

高性能聚酰亚胺气凝胶的制备进展

气凝胶是轻质开孔的介孔材料,由于其特殊的性质,如低密度(0.003~0.5g/cm3)、高孔隙率(70%~99.8%)、低介电常数(~1.1)、低热导率(最低为0.012W/(m·K))和高比表面积(100~1600m2/g),因此可应用于隔热材料、隔音材料、催化剂载体、药物缓释材料、低介电材料、吸附剂等。聚酰亚胺是一类重要的高性能聚合物,近些年,聚酰亚胺气凝胶备受重视。本文综述了现有多种聚酰亚胺气凝胶的制备方法及其优缺点,并对今后的研究工作进行了展望。