聚3-己基噻吩/碳纳米管薄膜的制备及电导性能研究

利用化学氧化法原位聚合制备了聚3-己基噻吩(P3HT)/多壁碳纳米管(MWNT)纳米复合薄膜。透射电子显微镜表明,MWNT在复合薄膜中的分散均匀性得到了提高;通过UV-Vis光谱证实了MWNT和P3HT之间存在着强烈的相互作用;四探针法测试表明,P3HT/MWNT纳米复合物具有半导体电导特征,最高电导率可达0.15 S/cm。     

Photoemission and conductivity measurement of poly(N‐methyl aniline) and poly(N‐ethyl aniline) films

The studies involve the X‐ray photoelectron spectroscopy (XPS) and conductivity measurements of poly(N‐methyl aniline) and poly(N‐ethyl aniline) films deposited electrochemically at different pH values of −0.96, 2.22, and 3.78 for N‐methyl aniline and 1.10, 2.22, and 3.78 for N‐ethyl aniline. The results obtained reveal significant differences in the film properties of the two matrices as a function of pH of solution. These differences are explained on the basis of the competitive reaction products formed during polymerization in the two matrices along with the differences in the electron‐donating ability of the methyl and ethyl groups present on the nitrogen (N) atom. These results are further supported by the UV–Visible and IR data. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1286–1292, 1999     

Temperature dependent electrical conductivity of p-doped poly(3,4-ethylenedioxythiophene) and poly(3-alkylthiophene)s

Summary Temperature dependent electrical conductivity of substituted polythiophenes (poly(3,4-ethylenedioxythiophene) PEDOTh and head-to-tail type poly(3-alkylthiophene) HT-P3RTh) has been measured. The electrical conductivity (σ) of p-doped PEDOTh and HT-P3RTh obeys equations of a type, ln σ= ln σ_o− (T_o/T)^0.25, with the T_o value of about 10⁵–10⁷ K. Received: 21 December 1998/Revised version: 8 February 1999/Accepted: 15 February 1999     

Electrical conductivity of poly(acrylic acid)–polyacrylamide complexes

The conduction mechanism in the interpolymer complex resulting from the interaction between poly(acrylic acid) (PAA) and polyacrylamide (PAAm) was investigated. The characteristic features of the relation between the logarithm of conductivity, log σ, and 1/T are different from those corresponding to the individual components of the complex. The value of σ for the complex was found to be less than its corresponding values for PAA or PAAm. The effects of the weight fraction of each polymer and the ionic strength of the solutions on the conductivity of the complex were also studied. The data showed that the σ of the complex depends on the weight fraction of the polymers. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 2049–2055, 1998     

Structure and conductivity of multi-walled carbon nanotube/poly(3-hexylthiophene) composite films

This work reports a structure-property investigation of a conjugated polymer nanocomposite with enhanced conductivity. Regioregular poly(3-hexylthiophene) (rrP3HT) was used to prepare composites with thin, short, multi-walled carbon nanotube (MWNT) addition over a wide range of concentrations. Scanning and transmission electron microscopies demonstrated an excellent dispersion and good wetting properties within the carbon nanotube composites. Coated MWNTs showed superstructures of P3HT self-organized on nanotube surfaces. Changes in the long range order and on the self-ordered mesophase of the bulk material were investigated by infrared and Raman spectroscopies, differential scanning calorimetry and X-ray diffraction. Interplay between charge transport through the semiconducting polymer and carbon nanotube network increased the composite's conductivity after percolation to values close to 10⁻² S cm⁻¹.     

Langmuir and Langmuir–Blodgett films of low‐bandgap polymers

Low‐bandgap conjugated polymers have provided a considerable increase in organic photovoltaic efficiencies, however, an understanding of class‐specific nanostructures, necessary to further improve device qualities, remains scarce. Their self‐assembly and associated electronic behaviors in Langmuir?Blodgett (LB) films are used here to provide relationships specific to each polymer, clarifying their structure?property characteristics. The behavior of two low‐bandgap polymers based on cyclopentadithiophene (PCPDTBT) and dithienosilole (Si‐PCPDTBT) units in the Langmuir trough were investigated and it is shown that it is possible to fabricate nanostructured films of low‐bandgap polymers on solid substrates with the LB deposition technique. The polymers were mixed with amphiphilic molecules at well‐defined concentrations to improve the formation of the LB films. The polymers were also deposited by drop‐casting and LB techniques onto interdigitated electrodes to evaluate their electrical properties, and the LB films were characterized for their optical and morphological properties. It was found that both LB and drop‐cast films of PCPDTBT showed higher electrical conductivities than those of Si‐PCPDTBT. Importantly, LB films resulted in higher electrical conductivities – by an order of magnitude ? compared to their equivalent mixtures with stearic acid in drop‐cast films, although drop‐cast films without stearic acid gave higher conductivities. This fine‐tuning of the molecular architectures of the films is thus demonstrated to directly affect the physical properties and may lead to an improvement in device efficiencies in future applications. © 2018 Society of Chemical Industry     

Preparation of silk fibroin–poly(ethylene glycol) conjugate films through click chemistry

Azide silk fibroin (azido SF) and alkyne terminal poly(ethylene glycol) (PEG) 2000 (acetylene‐terminal PEG 2000) were synthesized. Azido SF was reacted with acetylene‐terminal PEG 2000 to produce films via a copper‐mediated 1,3‐cycloaddition (‘click’ chemistry) generating a triazole linkage as the networking forming reaction. Through click chemistry, novel silk‐based films with various weight ratios were prepared and investigated. Fourier transform infrared, X‐ray diffraction and differential scanning calorimetry analyses showed that the ordered association of the PEG molecules is strongly constrained by the presence of the SF molecules and crosslinking and that the presence of acetylene‐terminal PEG 2000 in the films induced crystallization to a β‐sheet of SF chains. Water content and contact angle measurements indicated that the hydrophilicity of the films increased compared with SF. SF–PEG films exhibited smooth and rough structures, depending on degree of crosslinking and on the weight ratio of SF and PEG, as shown by scanning electron microscopy. Copyright © 2011 Society of Chemical Industry     

Thermal analyses of poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate), and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)

Thermal analyses of poly(3-hydroxybutyrate) (PHB), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(HB–HV)], and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) [P(HB–HHx)] were made with thermogravimetry and differential scanning calorimetry (DSC). In the thermal degradation of PHB, the onset of weight loss occurred at the temperature (°C) given by T_o = 0.75B + 311, where B represents the heating rate (°C/min). The temperature at which the weight-loss rate was at a maximum was T_p = 0.91B + 320, and the temperature at which degradation was completed was T_f = 1.00B + 325. In the thermal degradation of P(HB–HV) (70:30), T_o = 0.96B + 308, T_p = 0.99B + 320, and T_f = 1.09B + 325. In the thermal degradation of P(HB–HHx) (85:15), T_o = 1.11B + 305, T_p = 1.10B + 319, and T_f = 1.16B + 325. The derivative thermogravimetry curves of PHB, P(HB–HV), and P(HB–HHx) confirmed only one weight-loss step change. The incorporation of 30 mol % 3-hydroxyvalerate (HV) and 15 mol % 3-hydroxyhexanoate (HHx) components into the polyester increased the various thermal temperatures T_o, T_p, and T_f relative to those of PHB by 3–12°C (measured at B = 40°C/min). DSC measurements showed that the incorporation of HV and HHx decreased the melting temperature relative to that of PHB by 70°C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 90–98, 2001     

Synthesis of poly(ester‐anhydride)s based on poly(ϵ‐caprolactone) prepolymer

The objective of this study was to prepare high molecular weight poly(ester‐anhydride)s by melt polycondensation. The polymerization procedure consisted of the preparation of carboxylic acid terminated poly(?‐caprolactone) prepolymers that were melt polymerized to poly(?‐caprolactone)s containing anhydride functions along the polymer backbone. Poly(?‐caprolactone) prepolymers were prepared using either 1,4‐butanediol or 4‐(hydroxymethyl)benzoic acid as initiators, yielding hydroxyl‐terminated intermediates that were then converted to carboxylic acid‐terminated prepolymers by reaction with succinic anhydride. Prepolymers were then allowed to react with an excess of acetic anhydride, followed by subsequent polycondensation to resulting high molecular weight poly(ester‐anhydride)s. Upon coupling of prepolymers, size exclusion chromatography analyses showed an increase from 3600 to 70,000 g/mol in number‐average molecular weight (M_n) for the 1,4‐butanediol initiated polymer, and an increase from 7200 to 68,000 g/mol for the 4‐(hydroxymethyl)benzoic acid‐initiated polymer. 4‐Hydroxybenzoic acid and adipic acid were also used as initiators in the preparation of poly(?‐caprolactone) prepolymers. However, with these initiators, the results were not satisfactory. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 176–185, 2001     

Effect of spreading solvents on Langmuir monolayers and Langmuir–Blodgett films of PS-b-P2VP

Langmuir monolayers of polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) diblock copolymers (with the same PS block length and different P2VP block lengths) formed at the air/water interface were characterized with the Langmuir film balance technique. Nonselective and selective solvents were used to spread the samples on the water surface and the spreading solvents showed large effect on the surface pressure–molecular area isotherms. The corresponding Langmuir–Blodgett (LB) films of the samples were characterized with atomic force microscopy. The LB films transferred from the Langmuir monolayers spread with a nonselective solvent only exhibited isolated circular micelles, while those with a selective solvent exhibited quite different morphologies including planar structure, rodlike structure, circular micelles, and labyrinth pattern. As far as we know, the labyrinth pattern appears in the LB films for the first time.     

Characterization of poly(vinylpyrrolidone)–konjac glucomannan blend films

Blend films of konjac glucomannan (KGM) and poly(vinylpyrrolidone) (PVP) were prepared by using a conventional solvent‐casting technique and dried at room temperature. The structure and physical properties were studied by infrared spectroscopy (IR), wide‐angle X‐ray diffraction (WAXD), thermogravimetric analysis (TGA), differential thermal analysis (DTA), scanning electron microscope (SEM), and by measurement of mechanical properties. The changes of carbonyl stretching bands of KGM and PVP and hydroxyl stretching region of KGM were detected by FTIR analysis. WAXD analysis revealed that the film KP‐2 got the lowest crystallinity of all the films. The tensile strength and breaking elongation of the blend films reaches the maximum value at 10 wt % PVP content. The DTA curves indicated the existence of interaction between two kinds of macromolecules. Higher thermal stability was attained by konjac glucomannan through blending with PVP. These improvements are attributable to the existence of a certain degree of interaction between KGM and PVP molecules resulted from intermolecular hydrogen bonds. Air surface morphology of the films observed by SEM was consistent with the results mentioned above. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1049–1055, 2001     

Radiation-induced graft polymerization of acrylonitrile onto isotactic polypropylene and poly(tetrafluoroethylene–ethylene) copolymer films

Direct radiation-induced grafting of acrylonitrile (AN) onto both isotactic polypropylene (IPP) and (tetrafluoroethylene–ethylene) copolymer (ET) films has been studied. The effect of grafting conditions such as inhibitor and monomer concentrations and irradiation dose on the grafting yield was investigated. Homopolymerization of acrylonitrile was reduced to a minimum using ferric chloride (FeCl₃), and the suitable optimum concentration of the inhibitor was found to be 0.1 wt%. The higher the monomer concentration, the higher the degree of grafting obtained. It was observed that the degree of grafting onto IPP was higher than onto ET, at given grafting conditions. The effect of aging on IPP was also examined. IR spectroscopy showed that IPP was susceptible to photooxidation by aging. The swelling behaviour and electrical conductivity of the graft and hydrolysed graft films were investigated. The electrical conductivity was improved by hydrolysis of polyacrylonitrile in the graft chains.     

Synthesis and characterization of poly(oxyethylene)–poly(caprolactone) multiblock copolymers

Novel poly(oxyethylene)/poly(caprolactone) POE/PCL copolymers were synthesized by step growth polymerization of poly(ε-caprolactone) diols and poly(ethylene glycol) diacids using dicyclohexylcarbodiimide as coupling agent. The reaction was performed at room temperature and yielded multiblock copolymers with predetermined POE and PCL block lengths. The resulting copolymers were characterized by various analytical techniques including SEC, IR, ¹H NMR, DSC and X-ray diffractometry. Data showed that the properties of these polymers can be modulated by adjusting the chain lengths of the macromonomers. In particular, one or two crystalline structures can exist within the copolymers of various crystallinities. © 1998 SCI.     

Synthesis and characterization of poly(methylphenylsilylene)–poly(ethylene oxide) and poly(methylphenylsilylene)–polyisoprene multiblock copolymers

Multiblock copolymers were synthesized through condensation reactions of end‐groups of α,ω‐dichloro‐poly(methylphenylsilylene) with hydroxyl end‐groups of poly(ethylene glycol) or the chain‐ends of ‘living’ polyisoprenyl disodium. Optimum conditions have been sought through kinetic studies and by investigation of model reactions. The overall molecular weight distribution of poly(methylphenylsilylene)‐block‐poly(ethylene oxide) is characterized in terms of Flory's theory of condensation reactions, while the limiting step in the reaction is tentatively attributed to the formation of aggregates. © 2001 Society of Chemical Industry     

Miscible blends containing bacterial poly(3‐hydroxyvalerate) and poly(p‐vinyl phenol)

The miscibility of poly(3‐hydroxyvalerate) (PHV)/poly(p‐vinyl phenol) (PVPh) blends has been studied by differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy. The blends are miscible as shown by the existence of a single glass transition temperature (T_g) and a depression of the equilibrium melting temperature of PHV in each blend. The interaction parameter was found to be −1.2 based on the analysis of melting point depression data using the Nishi–Wang equation. Hydrogen‐bonding interactions exist between the carbonyl groups of PHV and the hydroxyl groups of PVPh as evidenced by FTIR spectra. The crystallization of PHV is significantly hindered by the addition of PVPh. The addition of 50 wt % PVPh can totally prevent PHV from cold crystallization. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 383–388, 1999     

Thermogravimetric analysis of poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)

The thermal degradation of poly(3‐hydroxybutyrate) (PHB) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) [P(HB‐HV)] was studied using thermogravimetry (TG). In the thermal degradation of PHB, the temperature at the onset of weight loss (T_o) was derived by T_o = 0.97B + 259, where B represents the heating rate (°C/min). The temperature at which the weight loss rate was maximum (T_p) was T_p = 1.07B + 273, and the final temperature (T_f) at which degradation was completed was T_f = 1.10B + 280. The percentage of the weight loss at temperature T_p (C_p) was 69 ± 1% whereas the percentage of the weight loss at temperature T_f (C_f) was 96 ± 1%. In the thermal degradation of P(HB‐HV) (7:3), T_o = 0.98B + 262, T_p = 1.00B + 278, and T_f = 1.12B + 285. The values of C_p and C_f were 62 ± 7 and 93 ± 1%, respectively. The derivative thermogravimetric (DTG) curves of PHB confirmed only one weight loss step change because the polymer mainly consisted of the HB monomer only. The DTG curves of P(HB‐HV), however, suggested multiple weight loss step changes; this was probably due to the different evaporation rates of the two monomers. The incorporation of 10 and 30 mol % of the HV component into the polyester increased the various thermal temperatures (T_o, T_p, andT_f) by 7–12°C (measured at B = 20°C/min). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2237–2244, 2001     

Thermal behavior of poly(acrylic acid)–poly(vinyl pyrrolidone) and poly(acrylic acid)–metal–poly(vinyl pyrrolidone) complexes

Thermal analysis (TGA and DTA) of samples of PAA, PVP, PAA–PVP complexes, containing different weight fractions of PAA and ternary polymer–metal–polymer complexes, were studied. The activation energy parameters for the thermal degradation were also calculated. The study of the effect of FeCl₃, NiCl₂, and Ni(NO₃)₂ on the TGA and DTA curves of the complexes showed that the decompositions are dependent on the concentrations and the nature of the metal ions. The DTA traces of PAA–PVP complex containing FeCl₃, NiCl₂, and Ni(NO₃)₂ showed that the treatment of the complex with these metal ions causes considerable changes in the thermal decomposition of PAA–PVP complex. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4049–4057, 2006     

Tunable size and shape of conductive poly(N‐methylaniline) based on surfactant template and doping

Poly(N‐methylaniline) (PNMA) is one of the polyaniline derivatives with N‐substituted position. Polyaniline derivatives have attracted attention due to their higher solubility in common solvents than pristine polyaniline, but they still possess lower electrical conductivity. In this work, PNMA was synthesized via chemical oxidative polymerization in an ethanol–water system. The effect of surfactant type, namely anionic sodium dodecylbenzenesulfonate (SDBS), cationic cetyltrimethylammonium bromide and non‐ionic Tween20, on the electrical conductivity, doping level and morphology was investigated. PNMA prepared with the SDBS system possessed the highest electrical conductivity among the obtained PNMAs with and without surfactants. The effect of $N_{{\mathrm{\text{HClO}}}_4}$/N_NMA dopant mole ratios on the re‐doping, crystallinity, morphology and particle size was also examined. Using an $N_{{\mathrm{\text{HClO}}}_4}$/N_NMA mole ratio of 10:1 in the re‐doping process provided the highest electrical conductivity of 15.53 ± 2.5 S cm^?1, a doping level of 55.59%, along with hollow spherical particles with the thinnest membrane. Electron microscopy images revealed that the morphology of PNMA particles depended mainly on the surfactant type but not the $N_{{\mathrm{\text{HClO}}}_4}$/N_NMA mole ratio. © 2019 Society of Chemical Industry     

Biodegradable blends of high molecular weight poly(ethylene oxide) with poly(3‐hydroxypropionic acid) and poly(3‐hydroxybutyric acid): a miscibility study by DSC,DMTA and NMR spectroscopy

The miscibility of high molecular weight poly(ethylene oxide) blends with poly(3‐hydroxypropionic acid) and poly(3‐hydroxybutyric acid) (P(3HB)) has been investigated by differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA) and high‐resolution solid state ¹³C nuclear magnetic resonance (NMR). The DSC thermal behaviour of the blends revealed that the binary blends of poly(ethylene oxide)/poly(3‐hydroxypropionic acid) (OP blends) were miscible over the whole composition range while the miscibility of poly(ethylene oxide)/poly(3‐hydroxybutyric acid) blends (OB blends) was dependent on the blend composition. OB blends were found to be partly miscible at the middle P(3HB) contents (25 %, 50 %) and miscible at other P(3HB) contents (10 %, 75 % and 90 %). Single‐phase behaviour for OP blends and phase separation behaviour for OB blends were observed from DMTA. The results from NMR spectroscopy revealed that the two components in the OP50 blend were intimately mixed on a scale of about 35 nm, while the domain sizes in the OB blend with a P(3HB) content of 50 % were larger than about 32 nm. © 2000 Society of Chemical Industry     

All polymer PTC devices: Temperature‐conductivity characteristics of polyisothianaphthene and poly(3‐hexylthiophene) blends

The present article is concerned with the temperature‐conductivity characteristics of blends consisting of polyisothianaphthene (PITN) particles and a soluble poly(3‐hexylthiophene) (P3HT). PITN was synthesized by direct conversion of 1,3‐dihydroisothianaphthene (DHITN) monomer using N‐chlorosuccinimide (NCS) as an oxidation/dehydrogenation reagent. The high conductivity and thermal stability of the doped and dedoped PITN were confirmed. Microscopic investigation by scanning electron microscopy (SEM) showed that the as‐prepared PITN exhibited diversified shapes and sizes, with large rectangular particles having an average size of 2 ～ 5μm and fine round particles ranging from 0.1 to 0.3 μm. The PITN particles were blended with the chemically synthesized P3HT as a high conductivity component to improve the conductivity and simultaneously maintain the positive temperature coefficient (PTC) effect of the original P3HT near its melting point. The temperature‐conductivity characteristics for PITN‐P3HT blends with various PITN contents showed that a blend having both a high conductivity (nearly 3 ～ 4 orders higher than that of the original P3HT) and a good PTC intensity could be obtained with a PITN content of 20 ～ 25%. The different temperature‐conductivity behavior of P3HT blends filled with PITN as compared to other conducting particles, for example, carbon black, was explained by its unique dispersion structure due to a relatively higher adhesive interaction of PITN particles with the P3HT matrix during the precipitation process. The results from heating recycles revealed that the PTC effect of PITN‐P3HT blends was not just related to the conductivity decrease of the P3HT matrix, arising from the conformational change of the conjugated backbone during the melting, but also to the dilution effect of the conducting percolation network due to the mobility of PITN particles induced by the viscosity decrease of the P3HT matrix. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1848–1854, 2005