Polyaniline nanostructures (nanosheets, nanofibers, and nanoparticles) can be assembled at the organic/aqueous interface or in solution by controlling the diffusion rate and the polymerization induction time of aniline. The quality of polyaniline nanostructures is determined by the polymerization solution conditions. Polyaniline nanosheets formation mechanism was proposed. Under certain polymerization conditions, polyaniline nanofibers or/and nanoparticles were obtained.
A method to prepare shape‐changing nanospheres from liquid crystalline elastomers is reported. The nanosized colloids are prepared by a miniemulsion process. During this process, colloids are prepared from a liquid crystalline (LC) main‐chain polyester and subsequently crosslinked into a nanometer‐sized LC elastomer. The ability of these LC elastomers to change their shape at the phase transition temperature from the smectic A to the isotropic phase was detected by temperature‐dependent transmission electron microscopy. The phase transition‐induced shape change leads to strongly shape anisotropic nanosized elastomer particles.
A new donor–acceptor polymer based on 9,9‐dioctylfluorene is synthesized and tested in organic photovoltaic devices. Results show that the polymer exhibits good solubility in a range of organic solvents and has a high hole mobility. When blended with a PC70BM acceptor and fabricated into a bulk heterojunction, photovoltaic devices having a maximum power conversion efficiency (PCE) of 6.2% and a peak external quantum efficiency of 74% are created. Such efficiencies are realized without any necessity for solvent additives or thermal annealing protocols.
The synthesis and polymerization of novel diallyldimethylammonium ionic liquid monomers is described. A free‐radical polymerization follows a ring‐closing cyclopolymerization mechanism similar to the one observed previously for diallyldimethylammonium halides that leads to pyrrolidinium functional polymers. As previously observed in other families of polymeric ionic liquids, their physico‐chemical properties are seriously affected by the nature of the counter‐anion. As an example, the thermal stability increases following the trend SCN− < < < bis(trifluoromethane)sulfonamide. Interestingly, this polymerization route may lead to the synthesis of a new family of random copolymers that have a similar poly(diallyldimethylammonium) backbone and a mixture of counter‐anions determined by the comonomer selection.
The synthesis of water soluble star‐block copolypeptides and their encapsulation properties are described. The star‐block copolypeptides, obtained by ring‐opening polymerization of amino acid N‐carboxyanhydrides, consist of a PEI core, a hydrophobic polyphenylalanine or polyleucine inner shell, and a negatively charged polyglutamate outer shell. The encapsulation study showed that these water soluble, amphiphilic star‐block copolypeptides could simultaneously encapsulate versatile compounds ranging from hydrophobic to anionic and cationic hydrophilic guest molecules.
Here we report for the first time on phosphorylation of cotton cellulose using baker's yeast hexokinase and phosphoryl donor adenosine‐5′‐triphosphate. An enzymatic assay was adopted for determination of the degree of phosphorylation of cellulose. This functional modification of cellulose resulted in improved colorability and flame resistance.
Phosphorylated glucopyranose unit of cellulose. 相似文献
A dextran‐based dual‐sensitive polymer is employed to endow gold nanoparticles with stability and pH‐ and temperature‐sensitivity. The dual‐sensitive polymer is prepared by RAFT polymerization of N‐isopropylacrylamide from trithiocarbonate groups linked to dextran and succinoylation of dextran after polymerization. The functionalized nanoparticles show excellent stability under various conditions and can be stored in powder‐form. UV and DLS measurements confirm that the temperature‐induced optical changes and aggregation behaviors of the particles are strongly dependent on pH.
A novel method of macromolecule encapsulation using micron‐sized polymeric shells constructed with a photoactive azobenzene containing polyelectrolyte is discussed. Fluorescently labeled dextran molecules were encapsulated using light to remotely shrink and change the wall permeability of new polymeric hollow shells. We observed that the proportion of shells with dye encapsulated increased along with the duration of irradiation. Electron microscopy imaging illustrated significant changes in the surface roughness of shells after being exposed to light. Finally, this new system was shown to possess a high thermal stability.
A directed diffusion approach is used to create atomistic models of crosslinked epoxy. In polymerization‐based approaches for preparing epoxy model structures, conversions higher than 95% are difficult to achieve due to very slow diffusion of unreacted monomers and crosslinkers in the partially formed network. This problem is overcome by creating very long bonds in the polymerization stage, and then relaxing these to equilibrium values by using a directed‐diffusion‐based relaxation strategy. The method minimizes the use of custom code by relying on the in‐built functionality in LAMMPS package (S. Plimpton, J. Comput. Phys. 1995 , 117, 1). The approach allows for near‐complete conversion (≈99%) and the thermal and volumetric properties of the structures so prepared show good agreement with experimental data.
A class of cationic bottle‐brush polymers that show ionic strength‐dependent stimuli responsiveness is prepared. Brush polymers with norbornene as backbone and quaternary ammonium (QA)‐containing polycaprolactone copolymers as side chains are synthesized by a combination of ring‐opening metathesis polymerization, ring‐opening polymerization, and click reaction. In water with low ionic strength, brush polymers are soluble due to the strong electrostatic repulsion between cationic QA groups. As the addition of salt to increase ionic strength, single brush polymers undergo a transition from extended conformation to collapsed state and finally become insoluble in solution due to the screening effect of salts that yield the once‐dominant electrostatic interactions among QA species to hydrophobic–hydrophobic interactions.
Summary: Mesoporous silica was used as substrate for the grafting of alkyl halides initiators. The control over the surface‐initiated polymerization of styrene and MMA, in terms of molar mass and molar mass distribution, was successfully achieved using an ATRP mechanism. The occurrence of the polymerization inside the mesopores was confirmed by thermogravimetric analysis.
Transmission electron microscopy and schematic representation of mesoporous silica functionalized by the anchored iniator (left) and the grafted polymer (right). 相似文献
This article provides a comprehensive review of the synthesis, properties and applications of organometallic polymers of the transition metals. The different classes of organometallic polymers are described according to their structural make‐up, as well as by their methods of synthesis. A number of examples of each class are given to emphasize the richness and diversity in these areas of research. In addition to linear polymers, hyperbranched, crosslinked, star and dendritic polymers are also described. The properties that transition metal‐containing organometallic polymers possess, as well as the applications that these materials have found in various domains are highlighted.
The nucleophilic living ring‐opening polymerization of N‐substituted glycine N‐carboxyanhydrides using solid‐phase synthesis resins is reported. By variation of experimental parameters, products with near Poisson distributions are obtained. As opposed to reversible deactivation radical polymerization, the living polymerization is demonstrated to be viable to high monomer conversion and through multiple monomer addition steps. Successful preparation of a multiblock copolypeptoid is proof for a highly living and robust character of the solid‐phase peptoid polymerization.
A series of π‐conjugated polymers linked by benzocarborane (1,2‐(buta‐1′,3′‐diene‐1′,4′‐diyl)‐1,2‐dicarbadodecaborane) were synthesized via Sonogashira–Hagihara polycondensation reaction. The opened molecular structure of diiodo monomer containing benzocarborane resulted in fast polymerization and high molecular weights. The obtained polymers were fully characterized by 1H, 13C, and 11B NMR spectroscopies. UV‐vis absorption and photoluminescence studies revealed the acceptor‐profile of benzocarborane. Unlike the polymers linked by o‐carborane, these polymers exhibited strong luminescence in the solution state, presumably because the inductive effect of carborane is dominant, rather than cage‐π interactions.
The need to biofunctionalize polymer surfaces for targeted bio‐related applications continues to grow, and efforts designed to meet this need rely heavily on surface grafting or polymerization. In this study, we provide a viable alternative by demonstrating that the peptide segment of a polymer‐peptide conjugate can be selectively driven to the surface of polymer nano/microfibers during electrospinning due to contrast in polarizability. Judicious choice of the polymer sequence in the conjugate permits use of the conjugate with compatible fiber‐forming polymers. Here, we use a water soluble poly(ethylene oxide)‐containing conjugate in combination with a hydrophobic thermoplastic, poly(methyl methacrylate). Surface enrichment is measured by X‐ray photoelectron spectroscopy, and fiber morphology is investigated by electron microscopy. Microfibers generated from the blends examined here are largely resistant to long term water immersion and are thus suited as support scaffolds or filtration membranes.
Sixteen parallel polymerization reactions of 2‐ethyl‐2‐oxazoline have been performed at different temperatures in an automated synthesizer that allowed individual heating of each reactor. During the reactions samples were taken automatically, which were characterized by means of both online GPC and offline GC, in order to optimize the reaction temperature and to determine the activation energy of the polymerization.
Ferrocenylmethyl methacrylate (FMMA) is one of the very few metallocene‐based monomers that are promising candidates for truly living anionic polymerization. Nevertheless, FMMA homopolymers with a narrow polydispersity, or block copolymerization studies that result in satisfying blocking efficiencies, are unknown so far. Here we describe a procedure that leads to highly regular FMMA‐based polymers for the first time, characterized by polydispersity indices (PDI) of less that 1.05 and very high blocking efficiencies (>95%) in sequential copolymerization with styrene. Some of the obtained poly[styrene‐block‐(ferrocenylmethyl methacrylate)]s show unusual microphase morphologies, presumably the consequence of high Tgs causing ‘frustrated’ non‐equilibrium states.
We describe the fabrication of a biomimically designed superhydrophobic poly(ε‐caprolactone) surface, which was obtained using a modified electrostatic process. The fabricated surface exhibits a micron‐sized pyramid structure consisting of accumulated droplets and nanofibres. By using this simple one‐step process, we can achieve a superhydrophobic surface having both a high water contact angle and low threshold sliding angle, similar to that of the superhydrophobic plant leaf.
