Amphiphilic hybrid π‐conjugated polymers that have polyhedral oligomeric silsesquioxanes on their side chains have been successfully synthesized by the Sonogashira–Hagihara polycondensation reaction. The obtained polymers were studied with ultraviolet‐visible absorption and photoluminescence spectra. In these polymers, the π‐conjugation length was extended along the poly(p‐phenylene‐ethynylene) backbone. Furthermore, the content of the POSS substituents can influence the aggregation behavior of the polymers and subsequent luminescent properties.
An atomic force microscope in the compression mode was used to probe the nanomechanical response of single dendrimeric molecules, as well as dendrimer aggregates adsorbed on silicon surface. The force‐compression behaviour of individual, generation 5 poly(amido amine) (PAMAM) dendrimers was described by a Hertzian model for the deformation of elastic bodies. The modulus values obtained ranged between 700 MPa (single dendrimers) and 150 MPa (dendrimer aggregates).
A unique example of macromolecular self‐assembly, where a mono‐component homopolyimide bearing carboxy end‐groups spontaneously forms nanopartilces with novel dimple‐like morphology in a single good solvent, is presented. The self‐assembly process is dramatically affected by the solution concentration and the temperature. It is proposed that such an unexpected self‐assembly behavior is a synergistic result of the self‐complementary hydrogen bonding between carboxy end‐groups and the propensity to parallel packing of polyimide chains through aromatic interactions.
Laccase‐catalyzed oxidative polymerization of phenol and its derivatives has been performed in aqueous organic solvents at room temperature in air. Laccase derived from Pycnoporus coccineus efficiently induced the polymerization to produce polyphenols consisting of a mixture of phenylene and oxyphenylene units. The unit ratio of the polymer could be precisely controlled by selection of the solvent and the monomer substituent.
We report the formation of poly(propylene) spherical and ellipsoidal particles templated by carbon nanotubes via solution crystallization. With an increase in nanotube loading, the particle shape changes from sphere to ellipsoid. In the intermediate concentration range, both spherical and ellipsoidal shapes coexist. The particle size decreases with an increase in nanotube loading.
Multiwalled carbon nanotubes (MWNTs) have been introduced into blends of polycarbonate (PC) and poly(styrene‐acrylonitrile) (SAN) by melt mixing in a microcompounder. Co‐continuous blends are prepared by either pre‐compounding low amounts of nanotubes into PC or SAN or by mixing all three components together. Interestingly, in all blends, regardless of the way of introducing the nanotubes, the MWNTs were exclusively located within the PC phase, which resulted in much lower electrical resistivities as compared to PC or SAN composites with the same MWNT content. The migration of MWNTs from the SAN phase into the PC phase during common mixing is explained by interfacial effects.
Summary: New polymer gelators consisting of poly(propylene glycol) or poly(ethylene glycol) and L ‐lysine‐based low‐molecular‐weight gelators have been developed. These polymer gelators were synthesized according to a simple procedure with high reaction yield, and formed organogels in many organic solvents. The organogelation mechanism was proposed from the transmission electron microscopy and FTIR spectroscopy studies.
Structures of the polymer gelators synthesized here. 相似文献
One‐dimensional methyl orange fibrils can be easily prepared. They are stable in acidic aqueous solutions and soluble in neutral water. When used to synthesize conducting polymer microtubules, the fibrils act as “hard templates” formally but as “soft templates” effectively. Microtubular structures of polypyrrole, polyaniline, and poly(3,4‐ethylenedioxythiophene) have been achieved successfully via such water‐soluble versatile templates.
CdSe nanoparticles stabilized with the amphiphilic diblock copolymer polystyrene‐block‐poly(4‐vinylpyridine) were spread from toluene dispersion on the water surface. Monolayers could be transferred onto solid substrates using the Langmuir‐Blodgett technique. By means of atomic force and scanning electron microscopy highly symmetric ring and disk‐like structures with diameters ranging between 150 nm and 1200 nm were observed.
AFM image of a mixed monolayer of copolymer 12 and CdSe nanoparticles stabilized with polystyrene‐block‐poly(4‐vinylpyridine). 相似文献
Nanoscale fibers with embedded, aligned, and percolated non‐functionalized multiwalled carbon nanotubes (MWCNTs) were fabricated through electrospinning dispersions based on melt‐compounded thermoplastic polyurethane/MWCNT nanocomposite, with up to 10 wt.‐% MWCNTs. Transmission electron microscopy indicated that the nanotubes were highly oriented and percolated throughout the fibers, even at high MWCNT concentrations. The coupling of efficient melt compounding with electrospinning eliminated the need for intensive surface functionalization or sonication of the MWCNTs, and the high aspect ratio as well as the electrical and mechanical properties of the nanotubes were retained. This method provides a more efficient technique to generate one‐dimensional nanofibers with aligned MWCNTs.
Summary: The polymerization of ε‐caprolactone (CL) in the presence of HCl · Et2O by an activated monomer mechanism was performed to synthesize diblock or triblock copolymers composed of poly(ethylene glycol) (PEG) and poly(ε‐caprolactone) (PCL). The obtained PCLs had molecular weights close to the theoretical values calculated from the CL to PEG molar ratios and exibited monomodal GPC curves. We successfully prepared PEG and PCL block copolymers by a metal‐free method.
The non‐metal catalyzed living ring‐opening polymerisation of ε‐caprolactone by PEG. 相似文献
In this work, secondary reactions involved in the free radical polymerization of butyl acrylate are investigated using quantum chemistry. First, various backbiting reactions are studied by adopting a simplified molecular model suitable for treating long polymer chains. The predicted reaction kinetics suggest the possibility of a radical migration along the poly(butyl acrylate) (PBA) chain as a consequence of subsequent j:j + 4 hydrogen abstractions, which are characterized by a low activation energy. Moreover, branching propagation and β‐scission reactions originating from mid‐chain radicals are investigated using a complete PBA model composed of five monomer units. The reaction kinetics involving short‐branch radicals are also examined, and a novel backbiting step leading to the formation of short branches is proposed.
The identification and control of a critical stage of polyaniline “nanotube” self‐assembly is presented, namely the granular agglomeration or growth onto nanorod templates. When the synthesis pH is held above 2.5, smooth insulating nanorods exhibiting hydrogen bonding and containing phenazine structures are produced, while below pH 2.5, small 15–30 nm granular polyaniline nanoparticles appear to agglomerate onto the available nanorod surface, apparently improving conductivity of the resulting structures by three orders of magnitude. This finding affects both fundamental theories of polyaniline nanostructure self‐assembly and their practical applications.
The lithium salt of 2,6‐difluoro‐2′‐sulfobenzophenone was conveniently synthesized in one‐pot by reacting 2,6‐difluorophenyllithium with 2‐sulfobenzoic acid cyclic anhydride in THF at −70 °C whereafter the product crystallized out of solution. A poly(arylene ether) and a poly(arylene sulfide) were prepared by polycondensation reactions to demonstrate the reactivity and efficacy of this new monomer to produce sulfonated high‐molecular weight aromatic polymers for fuel cell proton‐exchange membranes. This work demonstrated that organolithium chemistry may offer versatile and straightforward pathways to new functional monomers with fluorine atoms activated for nucleophilic aromatic substitution reactions.
