pH‐responsive PHEMA‐based polymeric nanostructures were grown in a controlled manner by ATRP‐based surface‐initiated polymerization. Initiator nanopatterns were obtained on silicon wafers covered with OTS resists made by AFM scanning probe oxidation lithography. AFM images confirmed isolated grafting of stimuli‐responsive hedge and dot brush structures exhibiting dimensions corresponding to a few tens of chains.
A new strategy for the synthesis of polyamides from polyesters of hydroxyl‐containing amino acids using a multi O N acyl transfer reaction was developed. This original approach allowed the synthesis of three generations of polymers from the same starting monomer. The polymerization of N‐benzyloxycarbonyl‐serine and its γ‐homologated derivative provided the Z‐protected polyesters; then the water‐soluble polycationic polyesters were obtained by removal of the Z‐protecting group; and finally the polyamides were obtained by a base‐induced multi O N acyl transfer, both in aqueous or organic medium. The key step transfer reaction was monitored by the disappearance and appearance of characteristic NMR proton signals and IR bands of polyesters and polyamides.
The preparation of novel highly water‐soluble electrostatic complexes from C60‐anchored multi‐armed poly(acrylic acid)s and cationic porphyrin derivatives was demonstrated. The UV‐vis absorption and photoluminescence (PL) of these complexes show that the absorption of soret band exhibits a remarkable red shift and the emission of the Q band indicates an apparent quenching effect in comparison with that of the parent cationic porphyrin. These results imply a remarkable ground state and excited state interaction between the porphyrin ring and the C60 moiety.
In the present study, it has been demonstrated that polymers containing pendant hydroxyl groups can undergo photoinduced crosslinking upon irradiation in the presence of bifunctional benzodioxinone. Irradiation of the copolymers of 2‐hydroxyethyl methacrylate (HEMA) and methyl methacrylate (MMA) in dichloromethane and THF solutions or in films containing bisbenzodioxinone, namely 5‐[9‐(4‐oxo‐2,2‐diphenyl‐4H‐benzo[d][1,3]dioxin‐5‐yloxy) nonyloxy]‐2,2‐diphenyl‐4H‐benzo[d][1,3]dioxin‐4‐one resulted in the formation of insoluble networks. Model studies using monofunctional napthodioxinone, namely 7‐hydroxy‐2,2‐diphenyl‐4H‐naphtho[2,3‐d][1,3]dioxin‐4‐one, revealed that crosslinking occurs via inter‐chain ester formation between photochemically generated keten intermediates and pendant hydroxyl groups.
This communication details the successful synthesis of low polydispersity core cross‐linked star (CCS) polymers via DPE‐mediated polymerisation. We demonstrate the ability to produce poly(methyl methacrylate) and poly(acrylonitrile) CCS polymers that are currently inaccessible via the two most common non‐metal‐based controlled radical polymerisation techniques (NMP and RAFT polymerisations).
Polymer hydrogels with characteristics distinct from those of solid materials are one of the most promising candidates for smart materials. Here, we report that a nanocomposite hydrogel (NC gel) consisting of a unique polymer/clay network structure, can exhibit complete self‐healing through autonomic reconstruction of crosslinks across a damaged interface. Mechanical damage in NC gels can be repaired without the use of a healing agent, and even sections of NC gels separated by cutting, from whichever the same or different kinds of NC gel, perfectly (re‐)combine by just contacting the cut surfaces together at mildly elevated temperatures. In NC gels, the autonomic fusion of cut surfaces as well as the self‐healing could be achieved not only immediately after being cut but also after a long waiting time.
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 new route to high‐performance electrospun polymer fibers was developed using a self‐bundling electrospinning technique combined with post‐treatments such as stretching and annealing under conditions similar to those used for conventional fibers. Self‐bundled electrospun PAN fiber yarns were characterized by SEM, mechanical tests, polarized FT‐IR spectroscopy and WAXD. The obtained results revealed that the PAN nanofiber yarns possessed enhanced alignment, a higher degree of crystallinity and higher molecular orientation after treatments, resulting in a remarkable improvement in mechanical performance, approaching the strength value of the corresponding conventional fibers.
Summary: Dienic elastomers are highly sensitive towards oxidation. During UV exposure, both scission and/or recombination reactions compete which involves an evolution of the molecular structure of the material. We developed an in situ technique to monitor the viscoelastic property changes upon UV irradiation of polymers in a single experiment. We illustrated this photorheology technique in the case of two kinds of elastomers. From our findings, this method is assumed to bring significant new advantages.
Photograph of the photorheometer used in this study. 相似文献
Summary: A modified random phase approximation method with a cumulant expansion for the semi‐flexible structure factor of diblock copolymers was exercised to describe the phase separation behavior of semi‐flexible and polydisperse diblock copolymers. Scattering curves and spinodal diagrams were calculated applying monomer specific input parameters. The influence of polydispersity was included applying basic concepts of mathematical statistics utilizing several probability density distributions in the case of the two single blocks. In contrast to semi‐flexibility, the main effect of polydispersity was found to shift the spinodal up, thus to enlarge the range of existence of the homogeneous phase.
Twofold Schultz‐Zimm distribution of diblock copolymers. 相似文献
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.
General step‐growth polymerization systems of order 2 are considered, i.e., systems of type “AfiBgi”, and a fast algorithmic method is presented to compute, at a given degree of conversion, the MSD and the MWD. The complete distribution is calculated; not just statistical averages of the polymer population such as or . For the computation of the low‐ and intermediate size/weight parts of the distribution curves, a set of recurrence relations is used. The high‐molecular size/weight parts of the curves (right tails) are computed using an accurate approximation derived from generating functions. In a previous paper, we applied our method to general order‐1 systems, i.e., systems of type “Afi”.
Summary: The success of metathesis chemistry techniques has sparked a tremendous interest in polymer and material chemistry. This contribution provides an overview of the state of the art in ring opening metathesis polymerisation (ROMP). It is intended to provide the reader with useful information on the interplay of initiators, monomers, and reaction conditions, thus aiding polymer chemists to utilise the ROMP toolbox. Prominent and illustrative examples from current research are given in the article.
