线型与星型聚酰胺6-聚氨酯嵌段共聚物的性能比较

以聚醚多元醇(PPG)、二苯甲烷二异氰酸酯(MDI)以及己内酰胺为单体,在碱性催化剂条件下,通过单体浇铸(MC)工艺制备了线型和星型聚酰胺6/聚氨酯(PA 6-PU)嵌段共聚物。使用差热分析(DSC),扫描电镜分析(SEM)研究了两者的结晶和熔融行为以及微观结构,并进行了比较。研究发现,与线型PA 6-PU嵌段共聚物相比,随着PU组分含量的增加,星型PA 6-PU嵌段共聚物具有较高的熔融温度(Tm)和结晶温度(Tc),并且,两共聚物中的PU与PA的相容性好。比较两者的力学性能,结果显示,同等PU添加量时,星型PA 6-PU嵌段共聚物冲击性能的提高更为明显。     

Preparation,morphology and properties of acid and amine modified multiwalled carbon nanotube/polyimide composite

The precursor of polyimide, polyamic acid, was prepared by reacting 4,4′-oxydianiline (ODA) with 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA). Unmodified, acid-modified and amine-modified multiwall carbon nanotubes (MWCNT) were separately added to the polyamic acid and heated to 300 °C to produce polyimide/carbon nanotube composite. Scanning electron microscopic (SEM) and transmission electron microscopic (TEM) microphotographs reveal that acid-modified MWCNT and amine-modified MWCNT were dispersed uniformly in the polyimide matrix. The effect of the acid and amine-modified MWCNTs on the surface and volume electrical resistivities of MWCNT/polyimide composites were investigated . The surface electrical resistivity of the nanocomposites decreased from 1.28 × 10¹⁵ Ω/cm² (neat polyimide) to 7.59 × 10⁶ Ω/cm² (6.98 wt% unmodified MWCNT content). Adding MWCNTs influenced the glass transition temperatures of the nanocomposites. Modified MWCNTs significance enhanced the mechanical properties of the nanocomposites. The tensile strength of the MWCNT/polyimide composite was increased from 102 MPa (neat polyimide) 134 MPa (6.98 wt% acid modified MWCNT/polyimide composites).     

主链刚性对磺化聚芳醚砜电解质膜性能的影响

以六氟双酚A(HFBPA)、9,9′-双(4-羟苯基)芴(BHPF)、4,4′-二氟二苯砜及3,3′-二磺酸钠-4,4′-二氟二苯砜为原料,经高温缩聚成功合成了一系列磺化聚芳醚砜(SPAES),并通过改变BHPF及HFBPA的比例来调节聚合物主链的刚性。结果表明,随刚性组分BHPF含量的增加,SPAES膜吸水率及质子导电率降低、但在水中的稳定性增加。在BHPF与HFBPA的比例为1∶1及磺化度为50%(SPAES50-50)条件下,膜在60℃水中平面和厚度方向的尺寸变化分别为0.12和0.13,电导率达到0.137 S/cm,而经130℃高温水处理200 h后的失重率仅为7%,表明其有望在高温燃料电池中得到应用。     

笼型聚倍半硅氧烷增韧3层聚酰亚胺薄膜的制备与性能

以3,3′,4,4′-联苯四酸二酐(BPDA)-对苯二胺(PDA)/4,4′-二苯醚二胺(ODA)型聚酰亚胺为芯层,将2,2′-双(4-(4-氨基苯氧基)苯基)丙烷(BAPP)-BPDA型聚酰胺酸涂覆于芯层的上、下表面并热亚胺化得到3层聚酰亚胺薄膜。为提高3层聚酰亚胺薄膜的韧性,将降冰片烯二酸酐-马来酰亚胺基七异丁基聚倍半硅氧烷交替共聚物(poly(MIPOSS-alt-NA))作为BPDA的共单体引入到上、下表层的热塑性聚酰亚胺中。结果表明,当poly(MIPOSS-alt-NA)的质量分数为6.0%时,3层聚酰亚胺薄膜的断裂伸长率从7.2%提高到14.5%,热膨胀系数则从27.0×10-6 K-1降低至23.6×10-6 K-1,与铜箔制备的柔性覆铜板剥离强度达到12.0 N/cm,针对拉伸断面电镜照片的变化对增韧机理进行了分析。     

Thiazole Imide‐Based All‐Acceptor Homopolymer: Achieving High‐Performance Unipolar Electron Transport in Organic Thin‐Film Transistors

High‐performance unipolar n‐type polymer semiconductors are critical for advancing the field of organic electronics, which relies on the design and synthesis of new electron‐deficient building blocks with good solubilizing capability, favorable geometry, and optimized electrical properties. Herein, two novel imide‐functionalized thiazoles, 5,5′‐bithiazole‐4,4′‐dicarboxyimide (BTzI) and 2,2′‐bithiazolothienyl‐4,4′,10,10′‐tetracarboxydiimide (DTzTI), are successfully synthesized. Single crystal analysis and physicochemical study reveal that DTzTI is an excellent building block for constructing all‐acceptor homopolymers, and the resulting polymer poly(2,2′‐bithiazolothienyl‐4,4′,10,10′‐tetracarboxydiimide) (PDTzTI) exhibits unipolar n‐type transport with a remarkable electron mobility (μ_e) of 1.61 cm² V^?1 s^?1, low off‐currents (I_off) of 10^?10?10^?11 A, and substantial current on/off ratios (I_on/I_off) of 10⁷?10⁸ in organic thin‐film transistors. The all‐acceptor homopolymer shows distinctive advantages over prevailing n‐type donor?acceptor copolymers, which suffer from ambipolar transport with high I_offs > 10^?8 A and small I_on/I_offs < 10⁵. The results demonstrate that the all‐acceptor approach is superior to the donor?acceptor one, which results in unipolar electron transport with more ideal transistor performance characteristics.     

Intercalation behavior of polyimide/organoclay nanocomposites during thermal imidization

To understand the intercalation behavior of polyimide (PI)/clay nanocomposites during thermal imidization, two different types of poly(amic acid) (PAA) were synthesized, and the corresponding hybrids with organically treated clays (O-MMT) were also prepared. The changes in molecular structure of the polymer matrix, interlayer spacing, and fracture morphology with a series of thermal imidization steps were investigated. The PAA/clay nanocomposites initially showed two X-ray diffraction peaks, indicating two levels of intercalation. As the temperature at which the thermal imidization step was performed increased, the peak intensity of the higher angle peak increased, and it remained as a unique peak at 2θ=6.70 (d-spacing of 13.2 Å) for both PI(1), based on pyromellitic dianhydride (PMDA)+4,4′-oxydianiline (ODA), and PI(2), based on PMDA+4,4′-(9-fluorenylidene)-dianiline (9FDA). However, the lower angle peak became smaller and broader, and the angle became higher. This peak finally disappeared after thermal treatment at 300 °C for PI(1), but did not disappear completely for PI(2), although the peak showed a marked decrease in intensity and became broader.     

Synthesis and characterization of three-arm polyamide 6-polyurethane block copolymer by monomer casting process

Three-arm polyamide 6-polyurethane (PA 6-PU) block copolymers were synthesized using ε-caprolactam as a monomer, caprolactam sodium as a catalyst, and a three-arm carbamyl caprolactam terminated polyurethane (PU) prepolymer as macroactivator. The three-arm PU prepolymer was formed from polyether glycerol (PPG) and diphenyl methane-4,4′ diisocyanate (MDI). The block copolymers were obtained using the monomer casting process (MC) of ε-caprolactam at different content of three-arm PU prepolymer (5–20%). In increasing the content of the soft phase, in Fourier transform infrared (FTIR), a displacement was observed in the band at 1637 cm⁻¹, which is assigned to the amide I of polyamide 6 (PA 6) shifted to a higher wavenumber. This suggested an interaction between the amide group of the PA 6 and the urethane group of the PU. The effects of the PU prepolymer content on the mechanical properties of the block copolymers were investigated. The results showed that the impact strength of the block copolymers at 25 °C and −50 °C temperature could be significantly improved. The crystallization and melting behaviors, structure and thermal properties and morphological characteristic of the block copolymers were studied using the different techniques such as differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMTA) and scanning electronic microscopy (SEM).     

具有极低熔体黏度的苯乙炔封端热固性聚酰亚胺树脂

为了开发适于树脂传递模塑(RTM)成型的低熔体黏度热固性聚酰亚胺树脂,采用2,2′,3,3′-三苯二醚四甲酸二酐(3,3′-HQDPA)和3,3′,4,4′-三苯二醚四甲酸二酐(4,4′-HQDPA)的混合物与3种不同的二胺单体合成了3种系列的苯乙炔封端的热固性聚酰亚胺树脂,其中二胺为4,4′-二氨基二苯醚(ODA),4,4’-二氨基-2,2’-双三氟甲基联苯(TFDB)和2-苯基-4,4′-二氨基二苯醚(p-ODA)。文中系统地研究了酰亚胺预聚物的结构和相对分子质量对预聚物的聚集态结构、熔体黏度及对固化后薄膜的热性能、力学性能的影响。研究结果表明,与ODA和TFDB不同,p-ODA的特殊化学结构使得由它合成的酰亚胺预聚物(相对分子质量为750)表现为无定形态,并在低温区具有极低的熔体黏度。它在200℃至280℃区间内任意温度恒温2 h后,熔体黏度都低于1 Pa·s,更适宜RTM成型。     

均苯型聚酰亚胺耐溶剂纳滤膜的制备

两步法制备一种均苯型聚酰亚胺耐溶剂纳滤膜,重点研究热亚胺化进程对膜性能的影响.选用热亚胺化程序为200℃保持2.5h,250℃保持2 h,300℃保持2h.测试结果表明耐溶剂纳滤膜在大部分测试溶剂中有较好的稳定性,膜的几种纯溶剂通量均保持较高水平的同时对结晶紫和依来络蓝黑R水溶液的截留率分别达到99.8％和97.9％.     

Processing and properties of carbon fiber/Triple-A polyimide composites fabricated from imide oligomer dry prepreg

Triple-A polyimide (TriA-PI) concept, “amorphous, asymmetric, and addition type”, was originally proposed by Yokota in 1999 for high temperature polymer matrix composites. The first version polyimide “TriA-PI-1” was developed from a-BPDA (2,3,3′,4′-biphenyltetracarboxylic dianhydride), 4,4′-oxydianiline (4,4′-ODA), and phenylethynyl phthalic anhydride (PEPA). The cured polyimide exhibits excellent mechanical properties with high glass transition temperature.In this study, a new prepreg system, namely imide-oligomer dry prepreg was developed by impregnating imide-oligomer into unidirectional carbon fiber bundles directly. Carbon fiber/TriA-PI-1 composites were fabricated from the imide-oligomer dry prepreg, and mechanical properties were evaluated. It was demonstrated that the TriA-PI-1 composite exhibits excellent compressive and tensile strengths at 300 °C as well as room temperature. It was easy to make a high quality composite laminate without complicated process using imide-oligomer dry prepreg.     

Enhanced performance of 4,4′-bipyridine-doped PVDF/KI/I<Subscript>2</Subscript> based solid state polymer electrolyte for dye-sensitized solar cell applications

Pure (PVDF/KI/I₂) and 4,4′-bipyridine-doped PVDF/KI/I₂ solid state polymer electrolytes were prepared by solution casting method using N,N-dimethylformamide (DMF) as solvent. The solid state polymer electrolytes were characterized by the powder X-ray diffraction (PXRD), Fourier transform infrared (FTIR), AC-impedance, dielectric measurements and scanning electron microscopy (SEM) analysis. The crystallinity of the solid state polymer electrolytes was analyzed by PXRD measurement. The functional groups of the solid state polymer electrolytes were confirmed by FTIR analysis. The AC-impedance analysis was carried out to calculate the ionic conductivity of the solid state polymer electrolytes. The ionic conductivity value of pure (PVDF/KI/I₂) and 4,4′-bipyridine-doped PVDF/KI/I₂ solid state polymer electrolytes are 2.00?×?10^?6 S cm^?1 and 4.60?×?10^?5 S cm^?1, respectively. The dielectric properties of solid state polymer electrolytes were calculated by using the dielectric measurements. From the SEM analysis, the surface morphology of the solid state polymer electrolytes was analyzed. The power conversion efficiencies of pure (PVDF/KI/I₂) and 4,4′-bipyridine-doped PVDF/KI/I₂ solid state polymer electrolytes are 1.8% and 4.4%, respectively. 4,4′-bipyridine-doped PVDF/KI/I₂ solid state polymer electrolyte has higher power conversion efficiency due to its increased amorphous nature and ionic mobility.     

Synthesis and properties of sulfonated polyimide–polybenzimidazole copolymers as proton exchange membranes

Chemical stability of polymer electrolyte membranes (PEMs) is the key factor affecting the lifetime of fuel cells. It is greatly desirable to develop the PEMs with both high proton conductivity and excellent chemical stability. In this study, a series of sulfonated polyimide–polybenzimidazole copolymers (SPI-co-PBIs) are synthesized via random condensation polymerization of 1,4,5,8-naphthalene tetracarboxylic dianhydride, 4,4′-bis(4-aminophenoxy)biphenyl-3,3′-disulfonic acid, and an amine-terminated polybenzimidazole oligomer. The ion exchange capacities of the resulting SPI-co-PBIs are in the range 1.90–2.47 meq g^?1. Under fully hydrated condition, the SPI-co-PBI membranes show higher proton conductivities than Nafion112. It is found that the incorporation of a small fraction of PBI moiety into the polyimide structure resulted in significant improvement in radical oxidative stability. For example, the SPI-co-PBI-19/1 containing 5 mol % PBI moiety shows only 0.6 wt% weight loss after being soaked in the Fenton’s reagent (3 % H₂O₂ + 3 ppm FeSO₄) at 80 °C for 150 min, whereas the corresponding benzimidazole group-free sulfonated polyimide is completely dissolved in the Fenton’s reagent at 80 °C for 140 min. The SPI-co-PBI membranes also show excellent hydrolytic stability due to the highly stable ladder structure of the benzimidazobenzisoquinolinone linkages.     

One-step preparation of hierarchical porous carbons from poly(vinylidene chloride)-based block copolymers

A facile self-templating and activation-free method to fabricate the hierarchical porous carbons (HPCs) from poly(vinylidene chloride) (PVDC)-based block copolymers is reported in this article. A series of block copolymers consisted of PVDC and the polystyrene (PS) blocks were prepared via RAFT living radical polymerization. Effects of molar ratio between the PVDC and the PS blocks on the microphase separation and thermal degradation of the PVDC-b-PS copolymers, and the microstructure of the as-prepared porous carbons were investigated. The results show that the PVDC block acts as a good kind of carbon precursor capable of forming micropores (0.5–0.6 nm) due to the diffusion of small molecules eliminated during the degradation of the PVDC block, and the microdispersed PS block acts as a mesopore extender to generate the mesopores (3–30 nm) by the decomposition of the PS phase. The as-prepared HPCs have the unique structures with three-dimensionally interconnected micropores and mesopores. The high Brunauer–Emmett–Teller surface area (1220 m²/g) and total pore volume (0.92 cm³/g) were achieved through controlling the composition of block copolymer. The method is facile to prepare the HPCs and suitable to the PVDC-based copolymers with other pyrolyzable block.     

Thermal and fluorescent properties of optical brighteners and their whitening effect for pelletization of cycloolefin copolymers

The thermal and fluorescent properties of 4,4-bis(5-methyl-2-beazoxoazol)ethylene (Hostalux KS-N), 1,4-bis(benzoxazolyl-2-yl)naphthalene (Hostalux KCB), 2,5-bis-(5-tertbutylbenzoxazole-2-yl) thiophene (Uvitex OB), 2,2′-(4,4′-diphenolvinyl)dibenzoxazol (Uvitex OB-1), and 1,1′-biphenyl-4,4′-bis(2-(methoxyphenyl)ethenyl) (Uvitex 127) have been investigated. All of them exhibit good thermal stability (> 300 °C) and high fluorescent quantum yields (> 0.8). Furthermore, we also have successfully blended these optical brighteners into cycloolefin copolymers with the antioxidant (Irganox HP2921) to improve the discoloration after pelletization based on their whitening effect.     

含有氢键的聚酰亚胺薄膜的制备和性能表征

以对硝基苯甲酸为原料,通过酰氯化、酰化、还原反应成功合成了4,4’-二氨基苯酰替苯胺(DBN),DBN分别和3,3’,4,4’-联苯四酸二酐(BPDA)、均苯四甲酸二酐(PMDA)通过两步法缩聚制备出聚酰亚胺薄膜,用红外(FT-IR),差示扫描量热仪(DSC)和热重分析(TGA),拉伸测试表征其结构和性能,结果表明,成功合成了含有酰胺键的聚酰亚胺薄膜,并且酰胺键的N-H分别和酰亚胺环中的C-N和C=O形成了氢键。将其与4,4’-二氨基二苯醚(ODA)聚酰亚胺薄膜相比,对应二酐(BPDA和PMDA)分别和DBN制备的聚酰亚胺薄膜表现出了优异的热性能和耐溶剂性,尤其是拉伸强度有了显著的提高。     

聚芳醚砜醚酮共聚物的合成与表征

通过低温溶液亲电共缩聚合成了聚芳醚醚酮醚砜醚酮(Ia)、聚芳醚酮酮醚砜醚酮(Ib),甲基取代、双邻位甲基取代的聚芳醚酮酮醚酮醚砜醚酮(Ic、Id)等4种结构新型的共聚物。用傅里叶红外光谱仪(FT-IR)、核磁共振(1H-NMR)、差示扫描量热仪(DSC)、热重分析(TGA)、X射线衍射仪(WAXD)对聚合物进行了结构表征和性能测试。结果表明,共聚物有较高的玻璃化转变温度(Tg)177℃~188℃;较高的热分解温度(Td5%≥460℃),共聚物能溶解于N-甲基-2-吡咯烷酮,四氯乙烷和浓硫酸中;甲基取代的共聚物溶解性得到了明显改善,室温下还能溶于二氯甲烷、二氯乙烷、氯仿、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺中。     

Influence of preparation procedure and ferric oxide nanoparticles addition on transport properties of homogeneous cation-exchange SPPO/SPVC membrane

Homogeneous cation-exchange membranes were prepared through evaporation and phase inversion methods using sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) (SPPO) and sulfonated polyvinylchloride as binders. The effect of polymers blend’s ratio and preparation method on structure and electrochemical properties of the prepared membranes were evaluated. The microstructures of the membranes were investigated by scanning electron microscopy (SEM) and the sulfonation of polyvinylchloride was confirmed by elemental analyses. Moreover, the membranes performance was evaluated by ion-exchange capacity (IEC), fixed ion concentration, membrane potential, transport number, permselectivity, areal resistance, ionic permeability, flux of ions, current efficiency, membrane oxidative stability, mechanical properties and water content tests. The results indicated that IEC and water content were affected by the SPPO content and microstructures of the membranes. The results showed increased efficiency and suitable electrochemical properties for membranes prepared by the evaporation method in comparison with others. Also, \(\hbox {Fe}_{2}\hbox {O}_{3}\) nanoparticles were synthesized at room temperature by a simple sonochemical reaction between ferric chloride and NaOH. The results revealed that the addition of different amounts of \(\hbox {Fe}_{2}\hbox {O}_{3}\) nanoparticles to the polymeric matrix could affect the hydrophilicity and transport properties of ion-exchange membranes.     

星型嵌段共聚物PEO_4-b-PNIPAAm_4的合成

通过可逆加成-裂解链转移自由基聚合（RAFT）和活性阴离子开环聚合（ROP）方法合成了星型嵌段共聚物PEO4-b-PNIPAAm4。首先通过活性阴离子聚合合成了分子量为8000、分子量分布为1.1的四臂星型聚环氧乙烷（PEO4）,PEO4的末端羟基和DDAT进行酯化反应,得到大分子RAFT引发剂。然后引发N-异丙基丙烯...     

Properties of vacuum-deposited polyimide films

Vacuum-deposited polyimide (PI) thin films have been prepared by co-deposition of precursor pyromellitic dianhydride (PMDA) and 4,4′-oxydianiline (ODA) followed by thermal treatment. The dependency of the optical and electrical properties, chemical resistivity and mechanical stability on the composition (ODA:PMDA) and the degree of imidization of the PI layers have been investigated and discussed. The experimental results have yielded possibilities to microstructure the vacuum-deposited PI films by excimer laser irradiation or reactive ion etching in gas mixture CF₄/O₂.     

Heparin-containing block copolymers

Newly synthesized heparin-containing block copolymers, consisting of a hydrophobic block of polystyrene (PS), a hydrophilic spacer-block of poly (ethylene oxide) (PEO) and covalently bonded heparin (Hep) as bioactive block, were coated either onto glass, poly (dimethylsiloxane), polyurethane or PS substrates. Coated surfaces were characterized by determination of the surface-bound heparin activity, adsorption of AT III, plasma recalcification time assays, adhesion of platelets and by an ex vivo rabbit A-A shunt model.It was demonstrated that heparin was available at the surface of all heparin-bound surfaces to interact with AT III and thrombin and to prevent the formation of clots. The maximum immobilized heparin activity was found to be 5.5×10^-3 U cm^-2. Coated surfaces showed a significant prolongation of the plasma reclacification times as compared to control surfaces, due to surface-immobilized heparin. The platelet adhesion demonstrated that platelets reacted only minimally with the heparin-containing block copolymers in the test system and that the heparin-containing block copolymers seemed to passify the surface as compared to control surfaces. In the ex vivo A-A shunt experiments, which were carried out under low flow and low shear conditions, the heparin-containing block copolymers exhibited prolonged occlusion times, indicating the ability of the heparin-containing block copolymers to reduce thrombus formation at the surface.