多壁碳纳米管接枝超支化聚(胺-酯)

采用混酸氧化,使碳纳米管表面产生羧基,再分别以接出法(grafting from)的方式在碳纳米管表面长出超支化大分子;以接入法(grafting to)的方式将由一步法合成的超支化聚(胺-酯)通过酯化反应接枝到碳纳米管表面。通过SEM、FTIR、TGA-DSC以及XRD等表征手段并结合酸碱滴定法测定修饰后碳纳米管表面的羟基密度,对功能化修饰的碳纳米管进行分析。结果表明,分别以grafting from和grafting to方式接枝超支化聚(胺-酯)后,碳纳米管的羟基密度分别为24.74 mmol/g和20.04 mmol/g,修饰后的碳纳米管分散性能明显提高,同时末端丰富的官能团为碳纳米管的进一步功能化修饰创造了条件。     

Synthesis and characterization of poly(acrylonitrile-co-methylmethacrylate) nanocomposites reinforced by functionalized multiwalled carbon nanotubes

Polyacrylonitrile-co-poly(methylmethacrylate)/multiwalled carbon nanotubes (PAN-co-PMMA/MWCNTs) nanocomposites were synthesized by an in situ emulsifier-free polymerization method with variable percentages of functionalized carbon nanotube (f-MWCNT). MWCNTs were functionalized with concentrated H₂SO₄ and HNO₃ with a continuous sonication process. Chemical interaction of f-MWCNT with the copolymer was studied by UV-visible spectroscopy. Fourier transform infrared spectroscopy proved the interaction of f-MWCNT with the PAN-co-PMMA copolymer matrix. The structural interaction of f-MWCNT with copolymer matrix was investigated by X-ray diffraction study. The dispersion and morphology of the f-MWCNT in the copolymer matrix were studied by scanning electron microscopy and high-resolution transmission electron microscopy. It was noticed that the f-MWCNTs were uniformly dispersed within the copolymer matrix. The thermal property of the PAN-co-PMMA/f-MWCNT nanocomposite was analyzed by thermogravimetric analysis. It was noticed that the thermal stability of the PAN-co-PMMA/f-MWCNT nanocomposite was more than that of the virgin copolymer matrix. When the electrical conductivity property of the synthesized nanocomposite was measured, it was noticed that the better dispersion of f-MWCNT in the non-conductive PAN-co-PMMA copolymer matrix made the PAN-co-PMMA/f-MWCNT nanocomposites conductive. From the measurement of gas barrier properties of synthesized nanocomposites, it was assumed that the well-dispersed f-MWCNT in the copolymer matrix creates the huddles for penetration of oxygen gas. It was noticed that the oxygen permeability of the PAN-co-PMMA/f-MWCNT nanocomposite was reduced by five times as compared to that of the neat PAN-co-PMMA copolymer matrix. The PAN-co-PMMA/f-MWCNT nanocomposites with higher thermal stability and reduced oxygen permeability properties may be suitable for application as conducting packaging materials.     

The synthesis of functionalized carbon nanotubes by hyperbranched poly(amine-ester) with liquid-like behavior at room temperature

The solvent-free multi-walled carbon nanotubes (MWNTs) nanofluids are obtained through acid-base reaction and hydrogen bond roles with hyperbranched poly(amine-ester) (HPAE). MWNTs content is 16.8 wt%. The functionalized MWNTs exhibit liquid-like behavior in absence of solvent at room temperature. Correspondingly, the dense surface coverage is one modifying molecule per 30 carbon atoms on the surface of MWNTs. The functionalized MWNTs are soluble in good solvent of HPAE, but insoluble in non-solvent of HPAE. Their dispersibility, high thermal stability and ability to flow at room temperature make them attractive as lubricants, plasticizers and film-forming precursors.     

Surfactant assisted selective confinement of carbon nanotubes functionalized with octadecylamine in a poly(styrene-b-isoprene-b-styrene) block copolymer matrix

We report how dodecanethiol (DT) surfactant can be used as a good dispersant to solubilize octadecylamine functionalized single-walled carbon nanotubes (ODA-SWCNTs) in order to confine them in the polystyrene phase of the polystyrene-b-polyisoprene-b-polystyrene (SIS) block copolymer matrix. It has been also demonstrated how the block copolymer matrix is not able to self-assemble in ordered morphology when the ODA-SWCNTs are not modified with the surfactant. DT assisted confinement of carbon nanotubes into the PS phase causes not only the nanostructuration of the host polymer matrix but also switches the self-assembled nanostructure from ordered cylinders in the case of neat SIS to a self-assembled lamellar nanostructure.     

Viscoelasticity and thermal stability of poly(arylene ether nitrile) nanocomposites with various functionalized carbon nanotubes

Poly(arylene ether nitrile) (PEN) nanocomposites containing various functionalized multi‐walled carbon nanotubes (MWCNTs) were prepared through a solution‐casting method. The as‐prepared PEN nanocomposites were investigated using parallel‐plate rheometry and thermogravimetric analysis, aimed at examining the effect of surface functionalization on the dispersion of MWCNTs from the viscoelastic and thermal properties. The linear viscoelasticy results indicated that 4‐aminophenoxyphthalonitrile‐grafted MWCNTs presented better dispersion in the PEN matrix than purified and carboxylic MWCNTs because the corresponding composite showed the lowest rheological percolation threshold, which was further confirmed from scanning electron microscopy, dissolution experiments and solution rheological experiments. The thermogravimetric analysis results revealed that the presence of 4‐aminophenoxyphthalonitrile‐grafted and carboxylic MWCNTs retarded the depolymerization compared with purified MWCNTs, showing a marked increase in the temperature corresponding to a loss of 5 wt% (increased by 14–22 °C) and maximum rate of decomposition (increased by 4–8 °C). Both the state of dispersion and the surface functionalization of MWCNTs are very important to the thermal stability of the PEN matrix. Copyright © 2011 Society of Chemical Industry     

Single-walled carbon nanotubes functionalized with poly(nile blue A) and their application to dehydrogenase-based biosensors

This paper reports a new type of nanocomposite of poly(nile blue A) with single-walled carbon nanotubes (PNb-SWNTs). This nanocomposite was fabricated by the functionalization of SWNTs with poly(nile blue A), which was formed by electropolymerizing an Nb monomer through the use of cyclic voltammetry. Scanning electron microscopy (SEM), ultraviolet-visible spectroscopy (UV-vis), cyclic voltammetry and electrochemical impedance spectroscopy (EIS) were used to characterize the PNb-SWNTs. The cyclic voltammetric results indicated that PNb-SWNTs were able to electrocatalyze the oxidation of NADH at a very low potential (ca. −80 mV versus SCE) and lead to a substantial decrease in the overpotential by more than 700 mV compared with the bare glassy carbon (GC) electrode. A biosensor, ADH-PNb-SWNT/GC, was developed by immobilizing alcohol dehydrogenase (ADH) onto the PNb-SWNT/GC electrode surface. The biosensor showed electrocatalytic activity toward the oxidation of ethanol with a good stability, reproducibility, and higher biological affinity. Under optimal conditions, the electrochemical response to detect ethanol has the typical characteristics of Michaelis-Menten kinetics with an apparent Michaelis-Menten constant of  ∼ 6.30 mM, and depends linearly on the concentration of ethanol from 0.1 to 3.0 mM (with a correlation coefficient of 0.998), with a detection limit of ∼50 μM (at a signal-to-noise ratio of 3). The facile procedure of immobilizing ADH used in the present work can promote the development of electrochemical research for enzymes (proteins), biosensors, biofuel cells and other bioelectrochemical devices.     

Grafting of an aminated poly(phenylene sulphide) derivative to functionalized single-walled carbon nanotubes

An aminated poly(phenylene sulphide) derivative (PPS-NH₂) has been covalently anchored to the surface of epoxy and acid-functionalized single-walled carbon nanotubes (SWCNTs). The characterisation through Fourier transform infrared spectroscopy, nuclear magnetic resonance, thermogravimetric analysis and Kaiser test corroborated the success of the grafting reactions, and allowed the identification and quantification of the covalent moieties. Scanning and transmission electron microscopy indicated an increase in the bundle diameter of the SWCNTs upon anchoring of the polymer chains. The results showed that the storage modulus, glass transition temperature and electrical conductivity of the polymer were exceptionally enhanced by the attachment to the SWCNTs. In contrast, the crystallization and melting temperature, degree of crystallinity and crystal size considerably decreased, as revealed by differential scanning calorimetry and X-ray diffraction experiments, due to the inactive nucleating role of these SWCNTs and the intense restrictions on chain mobility imposed by the SWCNT–polymer interactions. Acid-functionalized SWCNTs were more effective for reinforcing PPS-NH₂ than epoxy-functionalized SWCNTs, attributed to the formation of a larger number of covalent bonds, albeit led to a smaller increase in the electrical conductivity of the polymer. The results herein offer useful insights into the development of multifunctional CNT-reinforced thermoplastic composites for a wide variety of applications.     

SAM-modified microdisc electrode arrays (MDEAs) with functionalized carbon nanotubes

The construction of a novel voltammetric transducer employing mixed acid-chopped, oxidatively modified, single-walled carbon nanotubes (HOOC-SWNT-COOH) covalently coupled to alkane thiol self-assembled monolayers (SAMs) that were deposited onto gold microdisc electrode arrays (MDEA-Au) (1296 microdiscs, 100 μm diameter each) has been demonstrated. The chemisorption of cysteamine (CA) and 11-amino-1-undecanethiol (11-AUT) SAMs onto the MDEAs resulted in MDEA-Au|CA and MDEA-Au|11-AUT, which when conjugated with the HOOC-SWNT-COOH produced MDEA-Au|CA|SWNT and MDEA-Au|11-AUT|SWNT electrodes. Electrodes were characterized by multiple scan rate cyclic voltammetry in the presence of ferrocene monocarboxylic acid and by AFM and compared. As expected, CA modification of MDEA-Au produced a disordered film that did not alter the effective surface area of the MDEA while 11-AUT modification resulted in passivation and a 50% reduction in effective surface area. The conjugation of the SWNT to the CA-modified and the 11-AUT-modified MDEA-Au surface returned well-resolved voltammograms with highest peak currents (I_pa = 5.54 × 10⁻⁴ A, I_pc = 2.34 × 10⁻⁴ A at 100 mV/s). The effective area of MDEA-Au|CA|SWNT was increased by 200% while that of MDEA-Au|11-AUT|SWNT was increased by 100%. AFM showed SWNTs to be vertically oriented on the CA-modified surface but to be horizontally arranged and bundled on the 11-AUT surface.     

Partial delamination of the organo-montmorillonite with surfactant containing hydroxyl groups in maleated poly(propylene carbonate)

Maleated poly(propylene carbonate) (PPC-MA)/organo-montmorillonite (OMMT) nanocomposites were first prepared via melt end-capping poly(propylene carbonate) (PPC) with maleic anhydride (MA) and melt-mixing the PPC-MA with commercial OMMT without and with hydroxyl groups in surfactants: Cloisite 20A (C20A) and Cloisite 30B (C30B), respectively. Intercalated and partially delaminated morphologies were corroborated via X-ray diffraction (XRD) and transmission electron microscopy (TEM). Dynamic mechanical analysis (DMA) revealed that PPC-MA was evidently reinforced by the partially delaminated C30B platelets. From XRD patterns of statically annealed PPC-MA/C20A and PPC-MA/C30B mixtures and Fourier transform infrared (FTIR) results of equivalent nanocomposites, partial delamination of C30B in PPC-MA was confirmed to be relevant to diffusion of PPC-MA molecular chains in C30B galleries, grafting of PPC-MA to C30B platelet surfaces and further separation of C30B platelets.     

Dispersion of non-covalently functionalized single-walled carbon nanotubes with high aspect ratios using poly(2-dimethylaminoethyl methacrylate-co-styrene)

Single-walled carbon nanotubes (SWCNTs) with high aspect ratios were well dispersed in organic solvents to form stable suspensions using poly(2-dimethylaminoethyl methacrylate-co-styrene) (poly(DMAEMA-co-St)). The polymeric dispersant poly(DMAEMA-co-St) was synthesized in various compositions by atom transfer radical polymerization. The structures and the compositions of the poly(DMAEMA-co-St) were confirmed by ¹H NMR spectroscopy. The stability and dispersion of the functionalized SWCNTs with high aspect ratios in suspension were observed by dispersion stability analysis, transmission electron microscopy, scanning electron microscopy, and atomic force microscopy. The existence of unbundled SWCNTs was confirmed by Raman and ultraviolet/visible/near-infrared spectroscopy. Finally, SWCNT transparent conductive films with high transmittances and low sheet resistances were prepared on a poly(ethylene terephthalate) substrate using a spin-coating method.     

Hydrogen-bond acidic functionalized carbon nanotubes (CNTs) with covalently-bound hexafluoroisopropanol groups

Hydrogen-bond acidic fluoroalcohol groups are directly attached to the backbone of single walled carbon nanotubes (SWCNTs) via carbon-carbon bonds without the introduction of intermediate heteroatoms. Hexafluoroisopropanol functional groups are exceptionally strong hydrogen-bond acids, and are added to the nanotube surface (via the substituted benzene para position) as 2-phenyl-1,1,1,3,3,3-hexafluoro-2-propanol (i.e., -(p-C₆H₄)C(CF₃)₂OH) using the aryl diazonium approach to create hydrogen-bond acidic carbon nanotube (CNT) surfaces. These groups can promote strong hydrogen-bonding interactions with matrix materials in composites or with molecular species to be adsorptively concentrated and sensed. In the latter case, this newly developed material could potentially find useful application in chemical sensors and in CNT-based preconcentrator devices for the detection of hydrogen-bond basic analytes such as chemical warfare agents and explosives, as has been demonstrated for fluoroalcohol-containing polymers.     

Preparation and characterization of functionalized carbon nanotubes/poly(phthalazinone ether sulfone ketone)s composites

Multiwalled carbon nanotubes (MWNT) were successfully functionalized with phthalazinone‐containing diamine (DHPZDA) groups by the amidation reaction. The morphologies and structures of the DHPZDA‐functionalized MWNT (MWNT‐DHPZDA) were characterized by scanning electron microscope, Fourier transform infrared, and Raman spectroscopy, revealing that the DHPZDA were covalently attached onto the surface of MWNT, and the weight gain due to the functionalization was determined by thermogravimetric analysis. The MWNT‐DHPZDA/poly(phthalazinone ether sulfone ketone)s (PPESK) composites with different filler content were prepared by the solution‐mixing method. MWNT‐DHPZDA can be uniformly dispersed in the matrix and the strong interfacial adhesion between two constituents was found, which resulted in obvious enhancements of the mechanical properties. For the composite with 1 wt% MWNT‐DHPZDA, the tensile strength and the Young's modulus are 102.1 and 1,974 MPa, about 1.65 and 1.72 times of the pure PPESK, respectively. Conductivity measurements indicate that a typical percolation transition behavior takes place for MWNT‐DHPZDA content in the range from 0.5 to 2 wt%. Additionally, introducing MWNT‐DHPZDA into PPESK is favorable to improvement of the thermal stability. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Tailoring in thermomechanical properties of ethylene propylene diene monomer elastomer with silane functionalized multiwalled carbon nanotubes

The incorporation of silane treated multiwalled carbon nanotubes (S‐MWCNTs) is used as an effective path for tailoring thermomechanical properties of ethylene propylene diene monomer (EPDM). In this study, S‐MWCNTs were introduced into EPDM using internal dispersion kneader and two roller mixing mill. By altering the mass ratio of S‐MWCNTs from 0 to 1, thermal conductivity, thermal stability and phase transition temperatures and their respective enthalpies are discussed of the fabricated nanocomposites. It is observed that silane modification improves their dispersion and increases the interfacial bonding between MWCNTs and polymer matrix. Scanning electron microscopy along energy dispersive spectroscopy analysis is performed to confirm the silane functionalized MWCNTs are selectively distributed in the host polymer. More importantly, an important increase in mechanical properties like ultimate tensile strength and hardness is achieved through introducing silane functionalized MWCNTs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43221.     

Nanocomposites of poly(vinylidene fluoride) with multiwalled carbon nanotubes

The preparation and characterization of nanocomposites of poly(vinylidene fluoride), PVDF, with acid treated multiwalled carbon nanotubes (MWCNT) with a wide composition range, from 0.1 to 5.0% MWCNT by weight, is reported. Effect of uniaxial orientation by zone drawing on these nanocomposites is discussed and compared with unoriented compression molded films. Static room temperature two‐dimensional wide angle X‐ray scattering and Fourier transform infrared spectroscopy were used for phase identification. Differential scanning calorimetry, polarizing optical microscopy, dynamic mechanical analysis (DMA), and thermogravimetic analysis (TGA) were used to study the thermal and mechanical properties. Incorporation of MWCNT into PVDF has no obvious effect in forming beta phase crystal in the PVDF/MWCNT bulk films, while zone drawing cause a significant alpha to beta transition in PVDF/MWCNT. Results indicate that MWCNTs act as nucleation agent during crystallization and slightly increase the degree of crystallinity of PVDF/MWCNT bulk films. TGA indicates the thermal stability is improved when MWCNT concentration increases for unoriented PVDF/MWCNT film. The modulus also increases significantly when MWCNT concentration increases. The glass transition temperature measured by the peak position of tanδ from DMA does not change with MWCNT concentration, but a slightly higher glass transition can be obtained by zone drawing. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Supercritical fluid process for the synthesis of maleated poly(vinylidene fluoride)

Poly(vinylidene fluoride) was grafted with maleic anhydride monomer via a free‐radical mechanism in supercritical carbon dioxide medium. The free‐radical initiator chosen for this study was benzoyl peroxide. The structure of the resultant copolymer pendant groups was determined by ¹H NMR spectroscopy to consist of individual succinyl anhydride functional groups. The degree of functionalization (graft level) was obtained by FTIR spectroscopy through the correlation of absorbance bands using standard samples. The FTIR analysis indicated increased graft level with monomer loading, reaction temperature, and treatment time; however, initiator loading and reaction temperature showed more‐complex behavior. Graft levels increased at moderate benzoyl peroxide initiator loadings (5.0 wt%) and decreased at the highest initiator loadings (10.0 wt%). POLYM. ENG. SCI., 45:631–639, 2005. © 2005 Society of Plastics Engineers     

Multiwalled carbon nanotubes incorporated bombyx mori silk nanofibers by electrospinning

In this work, the regenerated silk protein with multiwalled carbon nanotubes (MWNT) was successfully electrospun in formic acid to generate the hybrid silk nanofibers. The morphology, structure and mechanical properties of the resulting silk/MWNT hybrid nanofibers were characterized using field emission scanning electron microscope (FE-SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FI-IR), Raman spectroscopy, wide angle X-ray diffraction (WAXD) and tensile testing. Thermo analysis was also carried out. TEM results confirmed that MWNT were well incorporated into the silk fibers. Addition of MWNT into silk nanofibers resulted in an enhanced mechanical property depending on MWNT content.     

Towards optimization of functionalized single-walled carbon nanotubes adhering with poly(3-hexylthiophene) for highly efficient polymer solar cells

In this paper, we present the optimization of single-walled carbon nanotubes (SWCNTs) by acid-treatment, solution ultrasonication time and dispersion in photoactive layer for efficient organic solar cells. After non-covalently adhering with poly(3-hexylthiophene) (P3HT), pre-functionalized SWCNTs were blended into the composites of P3HT and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) as photoactive layer, and a maximum power conversion efficiency (PCE) of 3.02% with a short-circuit current density of 11.46 mA/cm² was obtained from photovoltaic cell indium-tin oxide (ITO)/poly(ethylene-dioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS)/P3HT:PCBM:SWCNTs/Al with an optimum 0.3 wt% SWCNTs in P3HT:PCBM:SWCNTs nanocomposite, the PCE can be enhanced by more than 10% as compared to the control device ITO/PEDOT:PSS/P3HT:PCBM/Al. The performance improvement by incorporating with functionalized SWCNTs is mainly attributed to the extension of excitons dissociation area and fastening charge carriers transfer across the active layer.     

CO_2/环氧丙烷共聚合成聚碳酸亚丙酯多元醇

利用双金属氰化物作为催化剂,催化CO2/环氧丙烷调节共聚制备聚碳酸亚丙酯多元醇(PPC),详细考察了催化剂用量、相对分子质量调节剂及其用量、CO2用量等对聚合的影响.研究发现PPC的相对分子质量与相对分子质量调节剂的用量成线性关系,可以根据需要合成具有规定相对分子质量的PPC树脂.最后提出聚合过程中碳酸丙烯酯可能按照解拉链的方式生成.     

Influence of different functionalized multiwall carbon nanotubes on the mechanical properties of poly(ethylene terephthalate) fibers

Master batches with four different kinds of functionalized multiwall carbon nanotubes (MWCTs) were prepared through the mixing of MWCTs with poly(ethylene terephthalate) (PET) (0.01 : 0.99 w/w) in trifluoroacetic acid/dichloromethane mixed solvents (0.7 : 0.3 v/v) followed by the removal of the solvents in the mixture by flocculation. The results of scanning electron microscopy showed that a good dispersion of MWCTs in PET was achieved. The reinforced fibers were fabricated by the melt spinning of PET chips with small amounts of the master batch and then further postdrawing. The optimal spinning conditions for the reinforcement of fibers were a 0.6-mm spinneret hole and a 250 m/min wind-up speed. Among the four master batches, the fibers obtained from PET/master batch B made by acid-treatment had the highest enhancement of mechanical properties. For a 0.02 wt % loading of acid-treated MWCT, the breaking strength of the PET/master batch B composite fibers increased by 36.9% (from 4.45 to 6.09 cN/dtex), and the initial modulus increased by 41.2% (from 80.7 to 113.9 cN/dtex). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Functionalization of multiwalled carbon nanotubes with amphiphilic poly(aspartic acid)

A new method to functionalize multiwalled carbon nanotubes (MWNTs) with amphiphilic poly(aspartic acid) was investigated. The amphiphilic polymer (PASP‐C16) was synthesized by thermal condensation and aminolysis by hexadecylamine, followed by hydrolysis of the remaining succinimide units in the polymer backbone. The functionalization of MWNTs was achieved by physical adsorption of the biopolymer onto the surfaces of MWNTs. Ultraviolet‐visible ( UV‐vis) spectra showed that the functionalized MWNTs had a good aqueous dispersity and solubility. The interaction of PASP‐C16 with MWNTs was investigated by analyzing X‐ray diffraction (XRD) patterns, circular dichroism (CD), spectra and high‐resolution transmission electron microscopy ( HRTEM ). From the XRD patterns, it can be known that the aggregate of PASP‐C16 due to intermolecular interaction between hexadecyl chains has been reduced when the polymer interacting with MWNTs. CD spectra indicated that the interaction of hexadecyl chains of PASP‐C16 with the wall of MWNTs is the major interaction between PASP‐C16 and MWNTs, and MWNTs were covered by the poly(aspatic acid) backbone. © 2010 American Institute of Chemical Engineers AIChE J, 2011