Studies on the synthesis of low molecular weight,one‐dimensional polyanilines prepared by fast emulsion polymerization using (n‐dodecylbenzenesulfonic acid)/HCl emulsifiers

Low molecular weight polyaniline nanotubes were prepared by fast emulsion polymerization in the presence of both n‐dodecylbenzenesulfonic acid (DBSA) and HCl(aq). The anilinium monomers associated with DBSA emulsifiers were found to self‐arrange into strands of associated cylindrical micelles before polymerization, as monitored by their optical activity and optical image. In the presence of some HCl(aq), the monomer‐associated cylindrical micelles expanded and the polymerization rate could be speeded up. It was found that the low molecular weight (viscosity‐averaged molecular weight) polyaniline obtained can easily lead to the formation of highly conductive, one‐dimensional nanotubes or nanofibers monitored by the variation of optical activities and λ_max of the UV–visible–near IR spectra during polymerization. The DBSA/HCl ratio played an important role in the eventual properties and morphologies of the one‐dimensional polyanilines, which can be illustrated by conductivity, SEM and transmission electron microscopy measurements. The resultant one‐dimensional polyaniline nanotubes can be arranged into a layered structure by orientation, illustrated by AFM and wide‐angle X‐ray diffraction. © 2012 Society of Chemical Industry     

Short polyaniline nanorod prepared in the presence of para‐phenylenediamine

para‐Phenylenediamines (pPDAs) were mixed with aniline to synthesize a low molecular weight, nanowired polyaniline via emulsion polymerization, which demonstrated smaller intrinsic viscosity. Fourier transform infrared‐spectra illustrated the presence of phenazines in the polymers in the presence of pPDA. Free carrier‐tails in UV‐Vis‐NIR spectra are still present but their numbers decreased with pPDAs. Scanning electronic microscopy and transmission electronic microscopy (TEM) images showed the neat PANINTs shrank significantly and became randomly distributed after dedoping but the diameters of the PANINT‐pPDAs decreased slightly. TEM micrographs demonstrated the hollow morphology for the neat PANINTs but that of PANINT‐pPDA was shorter, solid nanowires. X‐ray diffractions patterns illustrated a layered structure for neat PANINTs which own a long c‐axis, not found for PANINT‐pPDAs. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterization of poly(n‐undecyl isocyanate)/polyaniline polyblend

Poly(n‐undecyl isocyanate) (PUDIC)/n‐dodecylbenzenesulfonic acid (DBSA)‐doped polyaniline (PANIDBSA) polyblend was prepared and the effect of the H‐bonding between these two polymers on the compatibility, conjugation chain length of PANIDBSA, and helixity of PUDIC in the polyblend system were studied. The monomer and polymer were characterized by NMR spectra and the polyblend was analyzed by FTIR, UV–vis spectra, and wide‐angle X‐ray diffraction. It was found when the blend composition of the PUDIC was higher than 10%, the WAXD patterns demonstrated lower angle shifting for the peaks at around 2θ = 2–2.5°, referring to the distance between the layers of the layered structure of PANIDBSA crystalline with increasing PUDIC, indicating the expansion of the layered structure of PANIDBSA. The FTIR spectra illustrated the presence of an absorption peak at 1700 cm^?1 shift to higher wave number with PUDIC due to its H‐bonding with PANIDBSA. The UV–vis spectra of PANIDBSA described a blue‐shift of the λ_max with PUDIC, indicating that the presence of PUDIC in the polyblend system can interrupt and decrease the conjugation chain length of PANIDBSA. The optical activity of the helical PUDIC decreased notably with the presence of PANIDBSA, resulting from the reversed helical effect (de‐nature) of H‐bonding. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Formation mechanism of a nanotubular polyanilines prepared by an emulsion polymerization without organic solvent

A nanotubular polyaniline (PANINT) was prepared from a simple emulsified polymerization method without oil solvent present. A mechanism of the formation of the nano-fibers/tubes was proposed to show that it started with the connecting arrangement of the neighboring anilinium micelles before and during polymerization, which resulted in the formation of the intermediate morphology of centipedes converting into rod-like nanofibers later. The obtained PANINTs displayed not only nanofibrous structure but owned an unusual dispersing behavior in toluene. SEM and TEM showed the dendrite-like networks of nanofibers connected and glued together by the free (not complexed to polyaniline backbone) n-dodecylbenzene sulfonic acid (DBSA) molecules. After removing the free DBSA by acetone, the clear/well-defined empty nanotubes can be seen from TEM in the magnified micrograph. The Atomic force microscopic (AFM) microgaphs demonstrated the cottage like surface morphology of the un-perturbed PANINTs and the morphology was converted to an anisotropic/oriented rods after rubbing on the wet/cast PANINTs' dispersion of toluene before entire evaporation.     

Melt‐processed polyaniline nanofibers/LDPE/EAA conducting composites

The melt‐processable polyaniline nanofibers doped with superfluous dodecylbenzenesulfonic acid (PANI‐DBSA) were synthesized using the interfacial polymerization and thermal doping technique. Conducting composites composed of PANI‐DBSA nanofibers, low‐density polyethylene (LDPE), and ethylene‐acrylic acid copolymer (EAA) as compatibilizer were prepared by melt processing. The effects of PANI‐DBSA nanofibers on the electrical conductivity, and mechanical properties, and morphological structure of the composites were investigated. As a result, the conducting composites had lower percolation threshold (4 wt%) due to the easy formation of conducting paths for fibrillar‐like PANI‐DBSA in the LDPE matrix, which was also confirmed by the frequency dependence of the real part of the AC conductivity. The Scanning electron microscopy (SEM) images indicated that the PANI‐DBSA nanofibers were dispersed uniformly in the matrix. The mechanical properties of the composites were improved at the low PANI‐DBSA load (about 1 wt%), but they were deteriorated at high PANI‐DBSA content. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Effect of Ni2+ as a codopant on the structure,morphology, and conductivity of nanostructured polyaniline

One‐dimensional nanostructures of polyaniline (PANI) doped with (1S)‐(+)‐10‐camphorsulfonic acid (D‐CSA) alone and with NiCl₂ as a codopant were synthesized via in situ polymerization. PANI nanofibers with diameters of about 200 nm were formed when PANI was doped with D‐CSA only. When NiCl₂ was added as a codopant, the morphology of PANI obviously changed. The effects and related mechanisms were investigated by Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, inductively coupled plasma–atomic emission spectroscopy, and X‐ray diffraction, and the results indicated that Ni²⁺ destroyed the micelles' structure by chemical conjunction with ? SO₃H groups in camphorsulfonic acid (CSA) molecules, which were the key component in forming the CSA–aniline micelles. The combination between Ni²⁺ and SO in CSA with a lower addition of Ni²⁺ led to a reduction of CSA doping to PANI, but a higher loading of Ni²⁺ brought about the direct doping of Ni²⁺ to PANI, which caused a higher degree of doping and oxidation. The conductivity of PANI increased almost linearly with increasing Ni²⁺. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of polydiphenylamine/multi‐walled carbon nanotube composites

We describe the synthesis of methane sulfonic acid (MeSA)‐doped poly(diphenylamine) (PDPA) with carboxylic groups containing multi‐walled carbon nanotubes (c‐MWNTs) via in situ polymerization. Diphenylamine monomers were adsorbed on to the surface of c‐MWNTs and polymerized to form PDPA/c‐MWNT composites. SEM and TEM images indicated two different types of materials: the thinner fibrous phase and the larger globular phase. The individual fibrous phase had a diameter around 100–130 nm, which should be the carbon nanotubes (diameter 20–30 nm) coated with a PDPA layer. The structure of PDPA/c‐MWNT composites was characterized by FTIR, UV‐visible spectroscopy and X‐ray diffraction patterns. The electrical conductivities of PDPA/c‐MWNT composites were much higher than that of PDPA without c‐MWNTs. Copyright © 2006 Society of Chemical Industry     

Synthesis and characterization of organo‐attapulgite/polyaniline‐dodecylbenzenesulfonic acid based on emulsion polymerization method

Organo‐attapulgite (OAT) was obtained by pretreating attapulgite (AT) with hexadecyltrimethyl ammonium bromide (HDTMABr) and dodecylbenzenesulfonic acid doped polyaniline (PAn‐DBSA) (OAT/PAn‐DBSA) was synthesized by emulsion polymerization at different OAT weight ratios. The perhaps polymerization procedure was supposed. The chemical structure and electronic absorption of the composites was confirmed by FTIR and UV–Vis spectroscopy, respectively. According to the X‐ray diffraction (XRD) results, it can be concluded that HDTMABr and PAn‐DBSA was just adsorbed on the surface of AT during the cation‐exchange process and OAT respectively without destroying the crystalline structure of AT or OAT. The composites showed a higher thermal stability than pure PAn‐DBSA by introduction of OAT into this polymerization system by using TGA analysis. Morphologies of the samples were confirmed by TEM and it showed that OAT was dispersed well in organic solvent after AT was pretreated with HDTMABr. The morphologies of OAT/PAn‐DBSA also supported the perhaps formation procedure we hypothesized. The electrical conductivity of the composite decreased with increasing the feed weight ratios of OAT in this polymerization system. POLYM. COMPOS., 2008 © 2007 Society of Plastics Engineers     

Shielding and dielectric properties of sulfonic acid‐doped π‐conjugated polymer in 8.2–12.4 GHz frequency range

This article deals with dielectric and electromagnetic interference shielding properties of the polyaniline doped with dodecyl benzene sulfonic acid (DBSA) synthesized by microemulsion polymerization of aniline in aqueous solution of DBSA. Dielectric constant and shielding effectiveness due to absorption (SE_A) were calculated using S‐parameter obtained from the vector network analyzer in 8.2–12.4 GHz frequency range. Maximum SE_A of 26 dB (>99%) was achieved for polymer sample. The real part ε′ of complex permittivity shows small variation, whereas the imaginary part ε″ is found to decrease with the increase in frequency. Different formulations have been performed to see the effect of monomer to dopant ratio on intrinsic properties of polyaniline. Further characterization of polymer was carried out by UV–visible and thermal gravimetric analysis, whereas the conductivity measurements were carried out by the four‐probe method.© 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Fabrication of DBSA‐doped polyaniline nanorods by interfacial polymerization

An interfacial polymerization was used to fabricate dodecybenzenesulfonic acid (DBSA)‐doped polyaniline (DBSA‐PANI) nanorods with diameter range from 40 nm to 1 μm. The molar ratio of aniline to ammonium peroxydisulfate (APS), the concentrations of DBSA and reaction temperature had an effect on the morphology and size of products. It was found that lower concentration of DBSA and lower temperature will be helpful to the formation of rod‐like PANI nanostructures with a relative small diameter. UV–vis and FTIR measurements were used to characterize the chemical structure of the obtained samples. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermosensitive self‐assembly micelles from A2BA2‐type poly(N‐isopropyl acrylamide)2‐b‐Poly(lactic acid)‐b‐Poly(N‐isopropyl acrylamide)2 four‐armed star block copolymers and their applications as drug carriers

A novel A₂BA₂‐type thermosensitive four‐armed star block copolymer, poly(N‐isopropyl acrylamide)₂‐b‐poly(lactic acid)‐b‐poly(N‐isopropyl acrylamide)₂, was synthesized by atom transfer radical polymerization and characterized by ¹H‐NMR, Fourier transform infrared spectroscopy, and size exclusion chromatography. The copolymers can self‐assemble into nanoscale spherical core–shell micelles. Dynamic light scattering, surface tension, and ultraviolet–visible determination revealed that the micelles had hydrodynamic diameters (D_h) below 200 nm, critical micelle concentrations from 50 to 55 mg/L, ζ potentials from ?7 to ?19 mV, and cloud points (CPs) of 34–36°C, depending on the [Monomer]/[Macroinitiator] ratios. The CPs and ζ potential absolute values were slightly decreased in simulated physiological media, whereas D_h increased somewhat. The hydrophobic camptothecin (CPT) was entrapped in polymer micelles to investigate the thermo‐induced drug release. The stability of the CPT‐loaded micelles was evaluated by changes in the CPT contents loaded in the micelles and micellar sizes. The MTT cell viability was used to validate the biocompatibility of the developed copolymer micelle aggregates. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4137–4146, 2013     

Solution self‐assembly of tailor‐made macromolecular building blocks prepared by controlled radical polymerization techniques

This review describes the preparation of colloidal aggregates (spherical micelles, cylindrical micelles, polymer vesicles, multicompartment micelles, polyion complexes, schizophrenic micelles) using bottom‐up self‐assembly approaches. In particular, it focuses primarily on the self‐organization of well‐defined macromolecular building blocks (macrosurfactants, polysoaps, polyelectrolytes) synthesized by controlled radical polymerization techniques such as atom transfer radical polymerization, reversible addition fragmentation transfer polymerization and nitroxide‐mediated polymerization. The goal of this review is to highlight that these versatile techniques of polymer synthesis allow the preparation of unprecedented nanostructures in dilute solutions. Copyright © 2006 Society of Chemical Industry     

Effect of aniline‐formaldehyde resin on the reduced conjugation length of doped polyaniline: Thermal studies

A linear aniline‐formaldehyde resin (AF) complexed with different acids was successfully synthesized with the traditional way of polymerizing a novolac‐type phenolic resin. When the AF(DBSA)_1.0 (AF complexed with only HDBSA (n‐dodecyl benzene sulfonic acid)) was blended with PANI(DBSA)_0.5 (polyaniline doped only by HDBSA, the T_gs (glass transition temperatures) of the polyblends decreased with PANI(DBSA)_0.5, indicating the presence of the compatibility that can alter the doping condition of PANI(DBSA)_0.5 by changing the conjugation length. In the polyblend system, it was also confirmed when the polyblend of 50/50 showed a higher residue weight than the rest of polyblends after being heated up to 450°C. The λ_max of UV–vis spectra of PANI (DBSA)_0.5 demonstrates a red shifts indicating the secondary doping effect (increasing conjugation length) was recovered when PANI(DBSA)_0.5 was mixed with less than 50% of AF(DBSA)_0.5 (HCl)_0.5. Similar phenomenon of red shift was found for the blended samples of PANI(DBSA)_0.5/AF(DBSA)_1.0 at high temperatures. IR spectra revealed an alkyl affinity interaction is present between PANI(DBSA)_0.5 and AF(DBSA)_1.0 at room temperature and a strong and free localized polaron band appeared at high temperatures due to the recovery of secondary doping. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2120–2128, 2007     

Self‐assembled nanostructures: preparation,characterization, thermal,optical and morphological characteristics of amphiphilic diblock copolymers based on poly(2‐hydroxyethyl methacrylate‐block‐N‐phenylmaleimide)

A series of well‐defined amphiphilic poly[(2‐hydroxyethyl methacrylate)‐block‐(N‐phenylmaleimide)] diblock copolymers containing hydrophilic and hydrophobic blocks of different lengths were synthesized by atom transfer radical polymerization. The properties of the diblock copolymers and their ability to form large compound spherical micelles are described. Their optical, morphological and thermal properties and self‐assembled structure were also investigated. The chemical structure and composition of these copolymers have been characterized by elemental analysis, Fourier transform infrared, ¹H NMR, UV–visible and fluorescence spectroscopy, and size exclusion chromatography. Furthermore, the self‐assembly behavior of these copolymers was investigated by transmission electron microscopy and dynamic light scattering, which indicated that the amphiphilic diblock copolymer can self‐assemble into micelles, depending on the length of both blocks in the copolymers. These diblock copolymers gave rise to a variety of microstructures, from spherical micelles, hexagonal cylinders to lamellar phases. © 2013 Society of Chemical Industry     

Synthesis of pH‐ and temperature‐responsive chitosan‐graft‐poly[2‐(N,N‐dimethylamino) ethyl methacrylate] copolymer and gold nanoparticle stabilization by its micelles

Novel pH‐ and temperature‐responsive chitosan‐graft‐poly[2‐(N,N‐dimethylamino)ethyl methacrylate] (chitosan‐g‐PDMAEMA) copolymers were successfully synthesized by homogeneous atom transfer radical polymerization (ATRP) under mild conditions. Chitosan macroinitiator was prepared by phthaloylation of amino groups of chitosan and subsequent acylation of hydroxyl groups of chitosan with 2‐bromoisobutyryl bromide. The copolymers were obtained by ATRP of 2‐(N,N‐dimethylamino)ethyl methacrylate and they can self‐assemble into stable micelles in water. Hybrid micelles with a PDMAEMA corona incorporating gold nanoparticles (Au NPs) were prepared in situ via the reduction of HAuCl₄ with NaBH₄. The pH and temperature responses of the copolymer micelles and hybrid micelles were characterized using UV‐visible spectroscopy and dynamic laser light scattering. The morphology of the micelles was observed using transmission electron microscopy and atomic force microscopy. The PDMAEMA corona of the micelles acts as the ‘nanoreactor’ and the ‘anchor’ for the in situ formation and stabilization of Au NPs. Therefore, the spatial distribution of Au NPs within the micelles can be tuned by varying the temperature and pH value. Copyright © 2010 Society of Chemical Industry     

Self‐assembly micelles from novel tri‐armed star C3‐(PS‐b‐PNIPAM) block copolymers for anticancer drug release

Novel tri‐armed star polystyrene‐block‐poly(N‐isopropylacrylamide) block copolymers with trimesic acid as central molecules were synthesized by successive two‐step atom transfer radical polymerization, and confirmed by Fourier‐transform infrared spectra, ¹H nuclear magnetic resonance, and laser light scattering gel chromatography system. The copolymers could self‐assemble into spherical core‐shell micelles in aqueous media independent on drug loading. Physicochemical properties of the blank and drug‐loaded micelles were examined by surface tension, fluorescence spectroscopy, UV‐vis, transmission electron microscope, and dynamic light scattering measurements. The copolymer micelles exhibited thermo‐triggered phase transition, with low critical solution temperature of 33.7 and 34.6°C, varying with copolymer compositions. The critical aggregate concentrations were 11.62 and 47.61 mg L^?1, and hydrodynamic diameters from 200 to 220 nm. Water‐insoluble 10‐hydroxycamptothecine was encapsulated into the micelle aggregates to investigate the change in the resulting physicochemical parameters, thermo‐triggered in vitro drug release, and the applicability as drug targeting release carriers. MTT assays were carried out to uncover cytotoxicity of the newly developed micelle‐based drug formulations. © 2014 American Institute of Chemical Engineers AIChE J, 61: 35–45, 2015     

Poloxamer and gelatin gel guided polyaniline nanofibers: synthesis and characterization

A rapid polymerization technique was successfully employed to synthesize interconnected polyaniline (PANI) nanofibers using chemical oxidative polymerization inside a soft template. The thermoreversible hydrogels of Lutrol F 127 and gelatin were used as templates where the interstices present in the hydrogel were responsible for the formation of PANI nanofibers with a diameter in the range ca 70?75 nm and ca 50?55 nm respectively and several micrometers in length. The doped emeraldine salt of PANI was confirmed by Fourier transform infrared spectroscopy and ultraviolet–visible spectroscopy. The crystallinity of as‐synthesized PANI nanofibers for both cases was verified by an X‐ray diffraction study while thermogravimetric analysis was performed to compare the relative stability of the synthesized PANI nanofibers. The electrical conductivities of polymerized PANI are of the order of 10^?3 S cm^?1 and are compared with those of template fabricated PANI. The Lutrol F 127 gel guided PANI nanofibers showed a rectifying property while the gelatin gel guided PANI provided a simple ohmic nature. © 2013 Society of Chemical Industry     

Preparation of monodisperse fluorescent core–shell polymer microspheres with functional groups in the shell layer by two‐stage distillation–precipitation polymerization

Monodisperse crosslinked core–shell micrometer‐sized microspheres bearing a brightly blue fluorescent dye, carbazole, and containing various functional groups in the shell layers were prepared by a two‐stage distillation–precipitation polymerization in acetonitrile in the absence of any stabilizer. Commercial divinylbenzene (DVB), containing 80 vol.% of DVB, was polymerized by distillation–precipitation in acetonitrile without any stabilizer using 2,2′‐azobisisobutyronitrile (AIBN) as the initiator for the first stage of polymerization which resulted in monodisperse polyDVB microspheres used as the core. Several functional monomers, including 2‐hydroxyethyl methacrylate and acrylonitrile together with N‐vinylcarbazole blue fluorescent comonomer, were incorporated into the shell layers with AIBN as initiator during the second stage of polymerization. The resultant core–shell polymer microspheres were characterized using scanning electron microscopy, Fourier transform infrared spectroscopy, UV‐visible spectroscopy and fluorescence spectroscopy. Copyright © 2006 Society of Chemical Industry     

Poly (N‐methylaniline)/multi‐walled carbon nanotube composites—Synthesis,characterization, and electrical properties

This study described the synthesis of hydrochloric acid (HCl)‐doped poly (N‐methylaniline) (PNMA) with carboxylic groups containing multi‐walled carbon nanotubes (c‐MWNTs) via in situ polymerization. Based on the π–π electron interaction between c‐MWNTs and the N‐methylaniline monomer and the hydrogen bond interaction between the carboxyl groups of c‐MWNTs and imine groups of N‐methylaniline monomers, N‐methylaniline molecules were adsorbed on the surface of c‐MWNTs and polymerized to form PNMA/c‐MWNT composites. Scanning electron microscopy images showed that both the thinner fibrous phase and the larger block phase could be observed. The individual fibrous phases had diameters from several tens to hundreds of nanometers, depending on the PNMA content. Transmission electron microscopy proved that PNMA/c‐MWNTs composite fibrous phases were core (c‐MWNT)‐shell (PNMA) tubular structures. The structure of PNMA/c‐MWNT composites was characterized by FTIR, UV–vis spectra, and X‐ray diffraction patterns. The electrical conductivities of PNMA/c‐MWNT composites were much higher than that of PNMA without c‐MWNTs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2356–2361, 2006     

Fabrication of polymer‐dispersed liquid crystals with low driving voltage based on the thiol‐ene click reaction

Polymer‐dispersed liquid crystals (PDLCs ) with a well‐defined polymer matrix were successfully fabricated by the thiol‐ene click reaction based on poly(ethylene glycol) diacrylate (PEGDA ) and trimethylolpropanetris‐(3‐mercaptopropionate) (TMTP ). UV ?visible spectrophotometry, Fourier transform IR spectroscopy, SEM and polarized optical microscopy were employed to explore the PDLC films obtained. Electro‐optical properties were studied with a UV ?visible spectrophotometer. It was found that the PDLC films with optimal thiol content fabricated by the thiol‐ene click reaction showed high transmittance, low driving voltage and a low memory effect. It was concluded that the driving voltage change of PDLCs with different thiol concentrations was caused by the polymerization rate and the structure of the polymer matrix. © 2017 Society of Chemical Industry