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1.
Multiwalled carbon nanotubes (MWNTs) were functionalized by a free‐radical reaction of vinyltriethoxysilane and were blended with poly(urea urethane) (PUU) containing poly(dimethylsiloxane) as a soft segment. PUU was end‐capped with aminopropyltriethoxysilane (A‐silane) or phenyltriethoxysilane (P‐silane).A‐silane‐end‐capped PUU was covalently bonded to functionalized MWNTs, whereas P‐silane‐end‐capped PUU was noncovalently bonded to pristine MWNTs by a π–π interaction. Fourier transform infrared, Raman spectra, and thermogravimetric analysis confirmed the functionalization of MWNTs. The results showed that the optimal reaction time of the functionalization of MWNT was 8 h, and the organic content of the modified carbon nanotubes reached 35.22%. Solid‐state nuclear magnetic resonance and dynamic mechanical analysis were used to investigate the molecular structure and molecular mobility of the carbon‐nanotube/PUU nanocomposites. A‐silane PUU covalently bonded to MWNTs showed a considerable reduction in the molecular motion of the soft segment, which led to the glass‐transition temperature decreasing from ?117 to ?127 °C as MWNTs were incorporated. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6084–6094, 2005  相似文献   

2.
Summary: We report on a new route to synthesize polymeric carbon nanotube‐polyurethane (PU) nanocomposites. Multi‐walled carbon nanotubes (MWNTs) functionalized by chemical modification were incorporated as a crosslinker in prepolymer, which was prepared from a reaction of 4,4′‐methylene bis(phenylisocyanate) and poly(ε‐caprolactone)diol. The reinforcing effect of carbon nanotubes in crosslinked MWNT‐PU nanocomposites was more pronounced as compared to that in conventional MWNT‐PU nanocomposites. The optimum content of chemically modified MWNTs for crosslinking with polyurethane was determined to be approximately 4 wt.‐% in our samples, based on observation of a NCO peak in FT‐IR spectroscopy. MWNT‐crosslinked polyurethane containing 4 wt.‐% modified MWNTs showed the highest modulus and tensile strength among the composites and pure PU. The presence of functionalized MWNTs in the polymeric nanocomposite yielded enhancement in the thermal stability due to crosslinking of the MWNTs with PU.

Possible configuration for MWNT‐PU nanocomposite molecules and FT‐IR spectra of samples obtained during reaction of prepolymer with functionalized MWNTs (second step).  相似文献   


3.
Pristine multiwalled carbon nanotubes (P‐MWNTs) were functionalized with 4‐chlorobenzoic acid via “direct” Friedel‐Crafts acylation in polyphosphoric acid (PPA)/phosphorous pentoxide (P2O5) medium. The resultant 4‐chlorobenzoyl‐functionalized MWNTs (F‐MWNTs) were soluble in chlorinated solvents such as dichloromethane, chloroform, and carbon tetrachloride. A large scale of nylon 610/F‐MWNT composite could be conveniently prepared by in situ interfacial polymerization of 1, 6‐hexamethylenediamine (HMDA) in an aqueous phase, and sebacoyl chloride with F‐MWNTs in an organic phase. Similarly, nylon 610/P‐MWNT composite was also prepared for comparison. The state of F‐MWNTs dispersion in nylon 610 matrix was distinctively better than that of P‐MWNTs, which could be clearly discerned by both naked eye and scanning electron microcopy (SEM). As a result, the tensile strength of nylon 610/F‐MWNT composite was 4.9‐fold higher than that of nylon 610/P‐MWNT composite. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6041–6050, 2008  相似文献   

4.
Diels–Alder cycloaddition reactions were used to functionalize multiwalled carbon nanotubes (MWNTs) with 1‐benzocylcobutene‐1′‐phenylethylene (BCB‐PE) or 4‐hydroxyethylbenzocyclobutene (BCB‐EO). The covalent functionalization of the nanotubes with these initiator precursors was verified by FTIR and thermogravimetric analysis (TGA). After appropriate transformations/additions, the functionalized MWNTs were used for surface initiated anionic and ring opening polymerizations of ethylene oxide and ε‐caprolactone (ε‐CL), respectively. The OH‐end groups were transformed to isopropylbromide groups by reaction with 2‐bromoisobutyryl bromide, for subsequent atom transfer radical polymerization of styrene or 2‐dimethylaminoethyl methacrylate to afford the final diblock copolymers. 1H NMR, differential scanning calorimetry (DSC), TGA, and transmission electron microscopy (TEM) were used for the characterization of the nanocomposite materials. TEM images showed the presence of a polymer layer around the MWNTs as well as the dissociation of MWNT bundles. Consequently, this general methodology, employing combinations of different polymerization techniques, increases the diversity of diblocks that can be grafted from MWNTs. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1104–1112, 2010  相似文献   

5.
Polypropylene (PP) nanocomposites with three different functionalized‐multiwalled nanotubes (F‐MWNTs) are compared in terms of their thermomechanical properties, morphology, oxygen permeability, and optical transparency. The F‐MWNTs dodecanol‐MWNT, dodecylamine‐MWNT, and 1,1,1,3,3,3‐hexafluoro‐2‐phenyl‐2‐propanol‐MWNT were combined with PP to produce hybrid films. The variations of their properties with the matrix polymer F‐MWNT content are discussed. Transmission electron microscopy photographs show that most of the F‐MWNTs are dispersed homogeneously in the matrix polymer on the nanoscale, although some agglomerated F‐MWNT particles are formed. Even composites with low F‐MWNT contents (≤3 wt %) exhibit much better thermomechanical values than pure PP. The gas permeability of the hybrids was found to decrease linearly with increases in the F‐MWNT content of the PP matrix. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010  相似文献   

6.
In this work, pristine multiwalled carbon nanotubes (MWNTs) were functionalized by utilizing the free radicals generated through Bergman cyclization of enediyne containing compounds 3 . Polyesters were subsequently grafted from the surface of MWNTs through ring‐opening polymerization of ε‐caprolactone or lactide initiated by free hydroxy groups generated after hydrolysis of ester groups. Functionalized MWNTs were characterized with a variety of techniques, including TGA, NMR, IR, UV–vis, TEM, and Raman spectroscopy. After surface modification, MWNTs showed good solubility in common organic solvents and polymer solutions. Fabrication of MWNTs polymer nanocomposites was revealed through electrospinning with polycaprolactone. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010  相似文献   

7.
Polyaniline‐carboxylic acid functionalized multi‐walled carbon nanotube (PAni/c‐MWNT) nanocomposites were prepared in sodium dodecyl sulfate (SDS) emulsion. First, the c‐MWNTs were dispersed in SDS emulsion then the aniline was polymerized by the addition of ammonium persulfate in the absence of any added acid. SDS forms the functionalized counterion in the resulting nanocomposites. The content of c‐MWNTs in the nanocomposites varied from 0 to 20 wt%. A uniform coating of PAni was observed on the c‐MWNTs by field‐emission scanning electron microscopy (FESEM). The PAni/c‐MWNT nanocomposites have been characterized by different spectroscopic methods such as UV‐Visible, FT‐Raman, and FT‐IR. The UV‐Visible spectra of the PAni/c‐MWNT nanocomposites exhibited an additional band at around 460 nm, which implies the induced doping of the MWNTs by the carboxyl group. The FT‐IR spectra of the PAni/c‐MWNT nanocomposites showed an inverse intensity ratio of the bands at 1562 and 1480 cm?1 as compared to that of pure PAni, which reveals that the PAni in the nanocomposites is richer in quinoid units than the pure PAni. The increase in the thermal stability of conductivity of the nanocomposites was due to the network structure of nanotubes and the charge transfer between the quinoid rings of the PAni and the c‐MWNTs. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

8.
Polyoxymethylene (POM)/multiwalled carbon nanotubes (MWNTs) nanocomposites were prepared through a simple solution‐evaporation method assisted by ultrasonic irradiation. To enhance the dispersion of MWNTs in POM, MWNTs were chemically functionalized with PEG‐substituted amine (MWNT‐g‐PEG), which exhibited strong affinity with POM due to their similar molecular structure. The thermal conductivity and the mechanical properties of the composites were investigated, which showed that the thermal conductive properties of POM were improved remarkably in the presence of MWNTs, whereas reduced by using MWNT‐g‐PEG due to the heat transport barrier of the grafted‐PEG‐substituted amine chain. A nonlinear increase of the thermal conductivity was observed with increasing MWNTs content, and the Maxwell‐Eucken model and the Agari model were used for theoretical evaluation. The relatively high effective length factor of the composite predicted with mixture equation indicated that there were few entangles of MWNTs for the samples of MWNT‐g‐PEG in the composites. The mechanical strength of the composites can be improved remarkably by using suitable content of such functionalized MWNTs, and with the increase of the aliphatic chain length of PEG‐substituted amine, the toughness of the composites can be enhanced. Transmission electron microscope result indicated that MWNT‐g‐PEG exhibited strong affinity with POM and a good dispersion of MWNTs was achieved in POM matrix. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 905–912, 2010  相似文献   

9.
Summary: Covalent surface functionalization of carbon nanotubes with polypeptides is promising for possible medical applications. This work presents a graft‐from approach to perform the polypeptide modification of multiwalled carbon nanotubes (MWNTs). The raw MWNTs are first amine‐functionalized. The amine‐functionalized MWNTs are then used as the initiator to initiate the ring‐opening polymerization of γ‐benzyl‐L ‐glutamate N‐carboxyanhydride (BLG‐NCA), to result in the polypeptide‐grafted MWNTs. FT‐IR, XPS, and TGA data demonstrate that the functionalization is successful. The TEM images of the products show that the thickness of the polypeptide shell of the PBLG‐MWNT is about 4.5–22 nm. Using the facile route developed here, carbon nanotubes functionalized with other types of polypeptides can be easily fabricated using the corresponding NCAs.

Strategy for the polypeptide modification of multiwalled carbon nanotubes by a graft‐from approach.  相似文献   


10.
聚氨酯接枝多壁碳纳米管的制备及表征   总被引:3,自引:0,他引:3  
采用两步法成功地将聚氨酯分子链以共价键连接到碳纳米管表面. 首先将聚丙烯酰氯通过与强酸氧化后多壁碳纳米管表面产生的羟基及少量羧基之间的化学反应共价接枝到碳纳米管表面; 然后将接枝到碳纳米管表面的聚丙烯酰氯与端羟基聚氨酯发生酯化反应, 实现了聚氨酯对碳纳米管的表面共价接枝. 采用傅里叶变换红外光谱(FTIR)、透射电镜(TEM)、扫描电镜(SEM) 和热重分析(TGA)等对接枝后的产物进行了表征, 结果表明, 聚氨酯已共价接枝到碳纳米管表面, 被接枝的聚合物的含量接近90%.  相似文献   

11.
The functionalized multi‐walled carbon nanotubes (MWNT) had been prepared by free radical reaction with vinyltriethoxysilane. Polydimethylsiloxane (PDMS)‐based poly(urea urethane) (PUU) was also synthesized. PUU was further end‐capped with aminopropyltriethoxysilane (A‐silane), or with phenyltrimethoxysilane (P‐silane). Fourier transform infrared (FTIR), Raman spectra and thermogravimetric analysis (TGA) confirmed the functionalization of MWNT. The Mn and Mw of PUU were 85,123 and 235,876 g/mol, respectively. Both A‐silane end‐capped PUU and P‐silane end‐capped PUU showed improved dispersion of MWNT compared with that of PUU and MWNT. Moreover, the reduced discrepancy of surface electrical resistance of the two sides of the MWNT/PUU nanocomposite film was found due to the homogeneous dispersion of MWNT. The microwave absorption and tensile strength of MWNT/PUU were also improved by the well dispersion of MWNT in PUU matrix. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1096–1105, 2006  相似文献   

12.
Covalent functionalization of alkyne‐decorated multiwalled carbon nanotubes (MWNTs) with a well‐defined, azide‐derivatized, thermoresponsive diblock copolymer, poly(N,N‐dimethylacrylamide)‐poly(N‐isopropylacrylamide) (PDMA‐PNIPAM) was accomplished by the Cu(I)‐catalyzed [3 + 2] Huisgen cycloaddition. It was found that this reaction could simultaneously increase the molecular size and bonding density of grafted polymers when PDMA‐PNIPAM micelles were employed in the coupling system. On the other hand, attachment of molecularly dissolved unimers of high‐molecular weight onto the nanotube resulted in low‐graft density. The block copolymer bearing azide groups at the PDMA end was prepared by reversible addition–fragmentation transfer polymerization, which formed micelles with a diameter of ~40 nm at temperatures above its critical micelle temperature. Scanning electron microscopy was utilized to demonstrate that the coupling reaction was successfully carried out between copolymer micelles and alkyne‐bearing MWNTs. FTIR spectroscopy was utilized to follow the introduction and consumption of alkyne groups on the MWNTs. Thermogravimetric analysis indicated that the functionalized MWNTs consisted of about 45% polymer. Transmission electron microscopy was utilized to image polymer‐functionalized MWNTs, showing relatively uniform polymer coatings present on the surface of nanotubes. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7187–7199, 2008  相似文献   

13.
Multiwalled carbon nanotubes (MWNTs) were functionalized with 2‐hydroxyethyl benzocyclobutene (BCB‐EO) through a Diels–Alder cycloaddition reaction. The functionalized MWNTs were utilized for the surface initiated ring opening (ROP) catalyzed and anionic polymerization of ε‐caprolactone (ε‐CL) and ethylene oxide (EO), respectively. The kinetics of the ROP of ε‐CL was monitored through thermogravimetric analysis (TGA) which revealed that the polymerization proceeds very fast as compared to that of EO and that both polymerizations could be controlled with time. 1H NMR, Raman and FTIR spectroscopy, TGA, DSC, and transmission electron microscopy (TEM) were employed for the characterization of these polymer/CNT hybrids. DSC results showed that a remarkable nucleation effect is produced by MWNTs that reduced the supercooling needed for crystallization of both PεCL and PEO. Furthermore, the isothermal crystallization kinetics of the grafted PεCL and PEO was substantially accelerated compared to the neat polymers. The strong impact on the nucleation and crystallization kinetics is attributed to the covalent MWNT‐polymer bonding. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4379–4390, 2009  相似文献   

14.
The effects of quantity of graphene and carbon nanotube‐based fillers and their pendant functional groups on the shear properties of a thermoset epoxy were investigated. Two novel functionalized graphenes, one with epoxy functionality and the other with an amine, are synthesized for this purpose. Nanocomposites are prepared at concentrations of 0.5, 1, 2, 3, 5, and 10 wt % and the effects of functionalization on the homogeneity of dispersion and the shear mechanical properties are investigated. The properties of the epoxy nanocomposites containing epoxy‐ and amine‐functionalized graphene are compared with those containing graphene oxide, Claisen‐functionalized graphene, neat multiwalled carbon nanotubes (MWNTs), three types of epoxy‐functionalized MWNT (EpCNT), and the unfilled epoxy. One of the EpCNT ( EpCNT3 ) was found to increase the plateau shear storage modulus by 136% (1.67–3.94 MPa) and the corresponding loss modulus by almost 400% at a concentration of 10 wt %. Several other fillers were also found to increase shear properties at certain concentrations. A hybrid system of EpCNT3 and graphite was also studied, which improved the storage modulus by up to 51%. SEM images reveal a correlation between thorough dispersion of the additive and enhancement of shear modulus. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 997–1006  相似文献   

15.
Summary: Hyperbranched poly(urea‐urethane)‐functionalized multiwalled carbon nanotubes (MWNT‐HPUs) have been synthesized by a one‐pot polycondensation of tolylene 2,4‐diisocyanate and diethanolamine in the presence of MWNTs terminated with multiple hydroxy groups. FT‐IR, Raman, 1H NMR, and 13C NMR spectra reveal that the HPU trees are covalently grafted onto the MWNT surfaces. After a high density of HPU trees (83.5 wt.‐%) is attached to the MWNTs, core‐shell nanostructures with MWNTs as the core and the HPU trees as the shell are formed. A loose and uniform nanotube network can be observed by TEM, SEM, and AFM. The resulting MWNT‐HPUs are soluble in polar solvents such as dimethylformamide, dimethylacetamine, 1‐methyl‐2‐pyrrolidinone, and dimethyl sulfoxide.

Hyperbranched poly(urea‐urethane)s functionalized multiwalled carbon nanotubes.  相似文献   


16.
The poly(N‐vinylcarbazole)‐grafted MWNTs (MWNT‐PVK) hybrid materials were synthesized in the presence of S‐1‐Dodecyl‐S′‐(α, α′‐dimethyl‐α″‐acetic acid) trithiocarbonate (DDAT)‐covalently functionalized multiwalled carbon nanotubes (MWNT‐DDAT) as reversible addition–fragmentation chain transfer (RAFT) agent. Incorporation of the PVK moieties onto the MWNTs surface can considerably improve the solubility and processability of MWNTs. For all MWNT‐PVK hybrid materials, they are soluble in some common organic solvents such as toluene, THF, chloroform, DMF and others. In contrast to the UV/Vis spectrum of DDAT‐PVK, which was synthesized by use of DDAT as RAFT agent under the same synthetic condition, in the visible region, the absorption spectrum of MWNT‐PVK exhibited a typical electronic absorption characteristics of solubilized carbon nanotubes, in which the absorbance decreases gradually in the range of 350–600 nm. At the same level of linear transmission the MWNT‐PVK with 79.2% PVK moieties in the material structure possesses best optical limiting performance in comparison with the other MWNT‐PVK composites, MWNTs and C60. The significant NLO responses manifest the MWNT‐PVK materials suitable candidate for viable optical limiting devices. Light scattering, originating from the thermal‐induced microplasmas and/or microbubbles, is responsible for the optical limiting. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3161–3168, 2010  相似文献   

17.
Multi‐walled carbon nanotubes (MWNTs) were functionalized with a silane coupling agent. The MWNTs were first coated with inorganic silica by a sol‐gel process and then grafted with 3‐methacryloxypropyltrimethoxysilane (3‐MPTS). The effect of raw MWNTs and silane‐functionalized MWNTs on the crystallization behavior of poly(propylene) (PP) was investigated by means of polarized optical microscopy, differential scanning calorimetry, and wide‐angle X‐ray diffraction. Results obtained from isothermal crystallization experiments indicate that 3‐MPTS functionalization affects the crystallization and melting behavior of PP/MWNTs composites remarkably, which can be attributed to the fact that 3‐MPTS functionalization of MWNTs leads to a uniform dispersion of MWNTs in PP matrix resulting in the good nucleating effect of MWNTs. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1616–1624, 2007  相似文献   

18.
Poly(lactic acid)‐grafted multiwalled carbon nanotubes (MWNT‐g‐PLA) were prepared by the direct melt‐polycondensation of L ‐lactic acid with carboxylic acid‐functionalized MWNT (MWNT‐COOH) and then mixed with a commercially available neat PLA to prepare PLA/MWNT‐g‐PLA nanocomposites. Morphological, thermal, mechanical, and electrical characteristics of PLA/MWNT‐g‐PLA nanocomposites were investigated as a function of the MWNT content and compared with those of the neat PLA, PLA/MWNT, and PLA/MWNT‐COOH nanocomposites. It was identified from FE‐SEM images that PLA/MWNT‐g‐PLA nanocomposites exhibit good dispersion of MWNT‐g‐PLA in the PLA matrix, while PLA/MWNT and PLA/MWNT‐COOH nanocomposites display MWNT aggregates. As a result, initial moduli and tensile strengths of PLA/MWNT‐g‐PLA composites are much higher than those of neat PLA, PLA/MWNT, and PLA/MWNT‐COOH, which stems from the efficient reinforcing effect of MWNT‐g‐PLA in the PLA matrix. In addition, the crystallization rate of PLA/MWNT‐g‐PLA nanocomposites is faster than those of neat PLA, PLA/MWNT, and PLA/MWNT‐COOH, since MWNT‐g‐PLA dispersed in the PLA matrix serves efficiently as a nucleating agent. It is interesting that, unlike PLA/MWNT nanocomposites, surface resistivities of PLA/MWNT‐g‐PLA nanocomposites did not change noticeably depending on the MWNT content, demonstrating that MWNTs in PLA/MWNT‐g‐PLA are wrapped with the PLA chains of MWNT‐g‐PLA. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

19.
Polypropylene-based nanocomposites filled with polypropylene-grafted multiwalled carbon nanotubes (PP-g-MWNT) were compared to PP samples filled with pristine MWNT. The effect of such additives on the structure and morphology of the polymer matrix was studied by small angle X-ray scattering (SAXS), wide angle X-ray diffraction (WAXD), polarized light optical microscopy (PLOM) and differential scanning calorimetry (DSC). PP-g-MWNT allowed a more efficient and unhindered crystallization at a lamellar level, while MWNT disrupted the order of lamellar stacks, probably because of their tendency to aggregate. A common trend of tensile properties and lamellar morphology as a function of filler content was noted in the series filled with functionalized carbon nanotubes.  相似文献   

20.
Poly(butylene terephthalate) (PBT) had been covalently attached onto the surface of multiwalled carbon nanotubes (MWNTs) by a “grafting from” method based on in situ ring‐opening polymerization (ROP) of cyclic butylene terephthalate oligomers (CBT) using MWNT‐supported initiator (MWNT‐g‐Sn). The Sn? O bond grafted on the surface of MWNTs, which was confirmed by X‐ray photoelectron spectroscopy, provided the initiating sites for ROP of CBT. Fourier transformed infrared spectroscopy and nuclear magnetic resonance were used to confirm the chemical structure of MWNT‐graft‐PBT copolymer and emission transmission electron microscope was utilized to observe the nanostructure of the PBT functionalized MWNTs. A distinct core–shell structure with PBT layer as the shell could be observed after functionalization of PBT despite it was not uniform. The results of thermogravimetric analysis indicated that the grafting ratio of PBT was about 59.3%. Furthermore, the solubility of the PBT functionalized MWNTs in phenol/tetrachloroethane had also been investigated. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

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