In situ grafting of carboxylic acid-terminated hyperbranched poly(ether-ketone) to the surface of carbon nanotubes

Carboxylic acid-terminated hyperbranched poly(ether-ketone)s (HPEKs) were successfully grafted onto the surfaces of single-walled carbon nanotube (SWNT) and multi-walled carbon nanotube (MWNT) to afford HPEK-g-SWNT and HPEK-g-MWNT nanocomposites. They were prepared via in situ polymerization of 5-phenoxyisophthalic acid as an AB₂ monomer for the HPEK in the presence of SWNT or MWNT in polyphosphoric acid (PPA)/phosphorous pentoxide (P₂O₅) medium. The resultant nanocomposites were homogeneously dispersed in various common polar aprotic solvents as well as in concentrated ammonium hydroxide. The experimental results from Soxhlet extraction, solubility enhancement, elemental analysis (EA), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM) provided clear evidences for grafting of hyperbranched polymers onto the surfaces of corresponding CNT's. Achieving enhanced solubility of CNT's in common organic solvents via the functionalization of CNT's is a key step for CNT's to be used in various application-specific purposes. The results could potentially envision to the area of CNT researches via the efficient introduction of three-dimensional globular dendritic macromolecules as increasing solubility, available multi-functionality, reactivity, processability, and also biocompatibility.     

Gas transport properties of 6FDA-TAPOB hyperbranched polyimide membrane

Physical and gas transport properties of the hyperbranched polyimide prepared from a triamine, 1,3,5-tris(4-aminophenoxy)benzene (TAPOB), and a dianhydride, 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), were investigated and compared with those of linear-type polyimides with similar chemical structures prepared from diamines, 1,4-bis(4-aminophenoxy)benzene (TPEQ) or 1,3-bis(4-aminophenoxy)benzene (TPER), and 6FDA. 6FDA-TAPOB hyperbranched polyimide exhibited a good thermal stability as well as linear-type analogues. Fractional free volume (FFV) value of 6FDA-TAPOB was higher than those of the linear-type analogues, indicating looser packing of molecular chains attributed to the characteristic hyperbranched structure. It was found that increased resistance to the segmental mobility decreases the gas diffusivity of 6FDA-TAPOB, in spite of the higher FFV value. However, 6FDA-TAPOB exhibited considerably high gas solubility, resulting in high gas permeability. It was suggested that low segmental mobility and unique size and distribution of free volume holes arising from the characteristic hyperbranched structure of 6FDA-TAPOB provide effective O₂/N₂ selectivity. It is concluded that the 6FDA-TAPOB hyperbranched polyimide has relatively high permeability and O₂/N₂ selectivity, and is expected to apply to a high-performance gas separation membrane.     

聚酰亚胺PI／SiC纳米复合材料的制备及特性

通过熔胶-凝胶方法合成了用于电子封装的聚酰亚胺PI/SiC复合薄膜介电材料,并通过扫描电镜、透射电镜、红外光谱对复合薄膜进行结构表征。结果表明,聚酰亚胺PI／SiC复合材料是一种共聚物,是纳米SiC粒子均匀分散在PI基体中的复合材料体系。在4284A型阻抗分析仪上测量了材料的电容,并换算出相应介电常数,最低达ε=2．0。     

Effect of the origin of ZnO nanoparticles dispersed in polyimide films on their photoluminescence and thermal stability

Polyimide (PI) films containing dispersed ZnO nanoparticles were prepared from both zinc nitrate hexahydrate (designated as Zn(NO₃)₂/PI) and ZnO nanoparticles, 2‐nm average primary size (ZnO/PI). This work shows how the origin of ZnO affects both the photoluminescence and thermal decomposition of the film. The presence of ZnO derived from Zn(NO₃)₂·6H₂O was confirmed by X‐ray diffraction technique. The fluorescent intensities from Zn(NO₃)₂/PI and ZnO/PI were much higher than that from pure PI films. When the ZnO concentration exceeded a certain saturation level, the emission intensity decreased due to the undesirable aggregation of ZnO. At the same concentration, ZnO/PI exhibited higher emission intensity than Zn(NO₃)₂/PI. All samples prepared under nitrogen emitted higher intensity than their counterparts prepared under argon. The ZnO/PI film was thermally more stable than the Zn(NO₃)₂/PI one. From TEM images of 117.6 mol% ZnO/PI films, the ZnO aggregates, whose average size was 17–90 nm, were well distributed throughout the film but poorly dispersed in nanometer range. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal and optical properties of hyperbranched fluorinated polyimide/mesoporous SiO2 nanocomposites exhibiting high transparency and reduced thermo-optical coefficients

A series of hyper-branched polyimide (HBPI)/mesoporous SiO₂ nanocomposite films were prepared from a fluorinated anhydride (6FDA), a fluorinated triamine (TFAPOB), and mesoporous SiO₂ nanoparticles (NPs). The anhydride-terminated precursor of HBPI was functionalized using a coupling agent prior to mixing with SiO₂ NPs. The morphologies and thermal-optical properties of the nanocomposite films were investigated, with particular focus on their optical transparency, refractive indices (n), and thermo-optical (TO) coefficients. The absolute values of TO coefficients (|dn/dT|) of HBPI film (50.8 ppm/K) were significantly reduced to 13.4 ppm/K by homogeneous dispersion of 15 wt% of SiO₂ NPs. The HBPI/SiO₂ composite films exhibited high thermal stability without significant weight loss of up to 400 °C in air. The films also exhibited small coefficients of linear thermal expansion (CTEs) within the range 30–40 ppm/K. In addition, enhanced interfacial interactions between SiO₂ and HBPI significantly improve the optical transparency with cutoff wavelengths shorter than 450 nm. The refractive indices of HBPI/SiO₂ composite films were found to range from 1.477 to 1.502, which agrees well with the calculated values. This study shows that the incorporation of SiO₂ NPs in multi-functional HBPI matrix is a promising approach to prepare high performance thermally stable films for thermo-optic applications.     

Synthesis and characterization of ZnS/hyperbranched polyester nanocomposite and its optical properties

The ZnS/hyperbranched polyester nanocomposite with higher refractive index was prepared by incorporating the acrylated 2-(2-mercapto-acetoxy)-ethyl ester-capped ZnS nanoparticles into the acrylated Boltorn™ H20 (H20). The acrylated 2-(2-mercapto-acetoxy)-ethyl ester-capped colloidal ZnS nanoparticles were synthesized by the reaction of zinc acetate with thioacetamide in N,N-dimethylformamide. The acrylated hyperbranched polyester was obtained by reacting acryloyl chloride with hydroxyl group of H20. The acrylated H20 plays an important role in stabilizing and dispersing ZnS nanoparticles with a diameter of 1-4 nm. The refractive indices of ZnS/hyperbranched polyester nanocomposites, depending on ZnS content, were determined to be in the ranges of 1.48-1.65.     

超支化聚酰亚胺的制备及其应用

综述了采用AB2型单体、A2 B3型单体、A2 B'B2型单体和AB AB2型单体合成超支化聚酰亚胺(HBPI)的制备方法,重点介绍了A2 B3型单体(包括二酐/三胺、二胺/三酐单体)制备HBPI的技术、HBPI的改性及应用领域和发展前景.HBPI具有较高的玻璃化转变温度和良好的溶解性能.     

Preparation and properties of organosoluble montmorillonite/polyimide hybrid materials

Organosoluble montmorillonite/polyimide hybrids were prepared using a monomer solution intercalation polymerization method. Montmorillonite was organo-treated with p-aminobenzoic acid and the organosoluble polyimide was based on pyromellitic dianhydride and 4,4′-diamino-3,3′-dimethyldiphenylmethane. The particle size of montmorillonite in the hybrid containing 1 wt % of montmorillonite is about 400 nm. The strength and the toughness of montmorillonite/polyimide hybrids are improved simultaneously when the montmorillonite content is below 5 wt %. The thermal stabilities of montmorillonite/polyimide hybrids are obviously improved and their thermal expansion coefficients are reduced. When the montmorillonite content is below 5 wt %, the montmorillonite/polyimide hybrids are soluble in strong aprotonic polar organic solvents. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2063–2068, 1999     

聚酰亚胺/纳米氧化硅氧化铝杂化膜的制备

研究了用溶胶凝胶法制得的二氧化硅及三氧化二铝溶胶,将其掺入到聚酰胺酸基体中,得到SiO2-Al2O3/聚酰亚胺杂化膜,并采用FTIR、SEM和TGA表征了所制备的杂化膜的结构微观形态和热性能。结果表明,薄膜材料中SiO2和Al2O3粒子分散均匀,与有机相存在键合,材料热分解温度有所提高。     

Structural,optical, cytotoxicity,and antimicrobial properties of MgO,ZnO and MgO/ZnO nanocomposite for biomedical applications

In this study, MgO nanoparticles were successfully fabricated and incubated inside ZnO NPs to form MgO/ZnO nanocomposite for biomedical applications. The x-ray diffraction analysis of MgO, ZnO, and MgO/ZnO has shown the single-phase x-ray diffraction patterns through X'pert High score. The crystallite sizes were calculated as 18 nm, 42 nm, and 53 nm, respectively. The average particle size of MgO, ZnO, and MgO/ZnO nanopowders depicted from secondary electron images of field emission electron microscopy were 56 nm, 400 nm, and 450 nm, respectively. The presence of MgO NPs inside ZnO NPs was confirmed by transmission electron microscopy. The elemental dispersive spectroscopy of MgO, given the peaks of oxygen and magnesium, also showed only zinc and oxygen peaks in ZnO, which confirms no other impurities in MgO and ZnO powders. The elemental analysis of MgO/ZnO nanocomposite showed the peaks of Zinc and Oxygen, along with a tiny peak of Mg. The photoluminescence and UV–vis spectroscopy revealed the absorbance fluorescence limit of the nanomaterials. Fourier transform infrared spectroscopy confirmed the several groups present in the nanocomposite. The biocompatibility of MgO, ZnO, and MgO/ZnO was observed with human peripheral blood mononuclear cells. The cytotoxicity studies were also performed against human cancer (liver and breast) cell lines. The MgO, ZnO, and MgO/ZnO exhibited the antimicrobial properties against Escherichia coli and Staphylococcus aureus.     

Growth and optical properties of ZnO nanorod arrays on Al-doped ZnO transparent conductive film

ZnO nanorod arrays (NRAs) on transparent conductive oxide (TCO) films have been grown by a solution-free, catalyst-free, vapor-phase synthesis method at 600°C. TCO films, Al-doped ZnO films, were deposited on quartz substrates by magnetron sputtering. In order to study the effect of the growth duration on the morphological and optical properties of NRAs, the growth duration was changed from 3 to 12 min. The results show that the electrical performance of the TCO films does not degrade after the growth of NRAs and the nanorods are highly crystalline. As the growth duration increases from 3 to 8 min, the diffuse transmittance of the samples decreases, while the total transmittance and UV emission enhance. Two possible nanorod self-attraction models were proposed to interpret the phenomena in the sample with 9-min growth duration. The sample with 8-min growth duration has the highest total transmittance of 87.0%, proper density about 75 μm⁻², diameter about 26 nm, and length about 500 nm, indicating that it can be used in hybrid solar cells.     

Wear,thermal, and physical properties of fluorine-containing polyimide/silica hybrid nanocomposite coatings

This study prepared fluorine and SiO₂ particles containing organic–inorganic hybrid polyimide nanocomposite coatings (PISFs) with inorganic content in the range of 5–20% in pure polyimide solutions via the sol–gel process. Polyimide hybrid structures containing fluorine and SiO₂ particles were synthesized by using perfluorooctyltriethoxysilane and tetraethyl orthosilicate. These formulations were applied on aluminum sheets by using a 75 μm wire wound applicator, and the coatings were cured for 8 h at room temperature and then 24 h at 100 °C. Increased inorganic contents caused slight decreases in the initial decomposition temperatures, but the char yield values increased for PISF15 and PISF20. All samples exhibited hydrophobic properties. When all samples were compared, PISF5 and PISF10 exhibited hydrophobicity, high wear resistance and thermal properties. Additionally, PISF5 and PISF10 showed high adhesion, hardness, and methyl ethyl ketone solvent resistance. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47399.     

纳米SiO2/聚酰亚胺复合薄膜的制备及性能的研究

以工业聚酰胺酸为原料,采用直接法制备了纳米SiO2/聚酰亚胺(PI)复合薄膜,通过红外光谱表征了亚胺化前后聚合物结构的变化,利用扫描电子显微镜观察了复合薄膜中SiO2的分散情况,测试了复合薄膜的拉伸强度,研究了纳米SiO2的加入对聚酰亚胺薄膜热稳定性的影响。     

Synthesis, optical and electrochemical properties of new hyperbranched poly(triphenylamine amide)s

A new triphenylamine-containing AB₂ type monomer with one carboxylic acid and two amino groups, 4-(bis(4-aminophenyl)amino)benzoic acid (3), was synthesized and used for the preparation of hyperbranched poly(triphenylamine amide)s. The self-polycondensation of the AB₂ monomer (3) afforded hyperbranched poly(triphenylamine amide) with amino end groups. The molecular weight of the hyperbranched poly(triphenylamine amide) was 21,000 Da determined by light scattering. End-capped hyperbranched polyamides were isolated by the chemical modification of unreacted amino groups with various acid chlorides. All the hyperbranched poly(triphenylamine amide)s exhibit excellent solubility in organic solvents such as NMP, DMF, DMSO, and DMAc at room temperature. The viscosities of hyperbranched poly(triphenylamine amide)s are as low as about 0.15 dL/g due to their dendritic structures. Poly(triphenylamine amide)s end-capped with rigid benzene ring have higher thermal stability than those with amino or aliphatic end groups. The photoluminescence of the hyperbranched polyamides is blue-yellow emissions around 430-510 nm. The energy gaps of the hyperbranched poly(triphenylamine amide)s with different end groups are about 2.93 eV and are independent on the end groups, but the HOMO and LUMO energy levels are dependent on the end groups.     

Facile preparation of highly luminescent CdTe quantum dots within hyperbranched poly(amidoamine)s and their application in bio-imaging

A new strategy for facile preparation of highly luminescent CdTe quantum dots (QDs) within amine-terminated hyperbranched poly(amidoamine)s (HPAMAM) was proposed in this paper. CdTe precursors were first prepared by adding NaHTe to aqueous Cd²⁺ chelated by 3-mercaptopropionic sodium (MPA-Na), and then HPAMAM was introduced to stabilize the CdTe precursors. After microwave irradiation, highly fluorescent and stable CdTe QDs stabilized by MPA-Na and HPAMAM were obtained. The CdTe QDs showed a high quantum yield (QY) up to 58%. By preparing CdTe QDs within HPAMAM, the biocompatibility properties of HPAMAM and the optical, electrical properties of CdTe QDs can be combined, endowing the CdTe QDs with biocompatibility. The resulting CdTe QDs can be directly used in biomedical fields, and their potential application in bio-imaging was investigated.     

Synthesis and second-order nonlinear optical properties of hyperbranched polymers containing pendant azobenzene chromophores

Two hyperbranched polymers with methyl ester (P1) and epoxy (P2) terminal groups containing pendant azobenzene chromophores were prepared through an “A₂ + B₃” approach used for second-order nonlinear optical materials. Their chemical structures were characterized by NMR and GPC analyses. The polymers have good solubility in common organic solvents and film-forming ability. The pure films were fabricated successively without doping into other matrices. The poled films exhibit high second-harmonic generation coefficients (>50 pm/V) due to the three-dimensional spatial isolation effect resulting from their highly branched structures. The optical nonlinearity of the poled P2 film is thermally more stable than that of P1 due to the cross-linking of epoxy groups with carboxylic acid groups in the former during poling. The onset decay temperature of SHG intensity of P2 was determined to be at around 155 °C, which was 20 °C higher than that of P1.     

Synthesis and properties of low‐color polyimide/silica hybrid films

A series of polyimide precursors, poly(amic acid)s, containing propyltrimethoxysliane at two chain ends were prepared from 4,4′‐bis(4‐amino‐2‐trifluoromethylphenoxy)biphenyl ( I ) with six commercially available dianhydrides, followed by end‐capping with 3‐aminopropyltrimethoxysilane (APrTMOS). A new class of fluorine‐containing polyimide/silica composite films ( III ) with chemical bonds between the fluorinated polyimide backbone and the silica network has been synthesized from the APrTMOS‐terminated precursors with tetramethoxysilane via the sol‐gel process and thermal cyclodehydration. The resultant hybrid films were light‐colored, flexible, and tough. They had high levels of thermal stability associated with high glass‐transition temperatures (>251°C), 10% weight‐loss temperatures in excess of 527°C, and char yields at 800°C in nitrogen higher than 60%. For a comparative study, the analogous nonfluorinated polyimide/silica hybrid films ( III′ ), based on 4,4′‐bis(4‐aminophenoxy)biphenyl ( I′ ), and the neat fluorinated polyimide films ( IV ), based on diamine I , were also synthesized and characterized. The hybrid films of the fluorinated series III showed a higher transparency and less color intensity when compared with the nonfluorinated III′ analogs. They also revealed a lower refraction index and birefringence than pure polyimides ( IV ). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4046–4052, 2007     

新型聚酰亚胺薄膜的制备及其性能研究

采用2,4,6-三甲基间苯二胺（TMmPDA）、4,4＇-二氨基二苯醚（DADPE）和3,3＇,4,4＇-四羧基联苯二酐（BP-DA）为主原料,摩尔比为1∶4∶5,合成得到了三甲基间苯二胺型聚酰胺酸（TMPAA）溶液,涂膜,热亚胺化,制得了三甲基间苯二胺型聚酰亚胺（TMPI）薄膜,并对其粘度、力学性能等进行了研究。     

Improved tribological properties of polyimide composites by micro–nano reinforcement

The hydroxylate carbon nanotubes (CNTs) were grafted by chemical method on the surface of the oxidized carbon fibers (CF) to improve the mechanical and tribological properties of polyimide (PI). The microstructure and fracture surface of the polyimide composites indicated that CF–CNTs hybrid as a multiscale reinforcement can distribute into the PI matrix homogeneously. Tribo-tests further showed that CF–CNTs hybrid had a better effect on hardness increment, impact strength enhancement, friction reduction, and wear resistance. Compared to the neat PI, the friction coefficient and wear rate of CF–CNTs/PI composite deceased by 23.2 and 55.9%, respectively. In particular, the loading capacity and high speed resistance of CF–CNTs/PI composite were greatly improved. The corresponding wear mechanisms were also discussed by observing the worn surface of the PI composites. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47900.     

Facile synthesis, high thermal stability, and unique optical properties of hyperbranched polyarylenes

New hyperbranched polyarylenes of high molecular weights are synthesized in high yields by copolycyclotrimerizations of diynes 1,4-diethynylbenzene, 4,4′-diethynylbiphenyl, 2,7-diethynylfluorene and 2,5-diethynylthiophene with monoynes 1-heptyne, 1-octyne and 1-dodecyne catalyzed by TaCl₅-Ph₄Sn in toluene. All the polymers show good solubility in common organic solvents, possess excellent thermal stability, and emit strong deep-blue lights of ∼400 nm with quantum efficiencies up to 98%. The polyarylenes effectively limit 532 nm lasers light, some of which show optical limiting performances superior to that of C₆₀, a well-known optical limiter.