Metal nanoparticles of various size and shape are prepared by the reduction of metal precursors in polymer micellar architectures (nanoreactors). The nanoreactors are developed from the amphiphilic invertible polyesters solved over a wide concentration range in solvents that strongly differ in polarity. In a non‐polar medium, the micelle core contains hydrophilic [poly(ethylene oxide)] fragments, which acts as a reducing agent of metal ions. Nanoparticle stabilization occurs because of the presence of hydrophobic (polymethylene) fragments outside of the micelle structure. The size and shape of the nanoreactors may be altered by the polyester composition and molecular weight as well as by the solvent polarity and concentration of the amphiphilic polyester.
A novel phenylacetylene ( 1 ) having two hydroxyl groups and a chiral pinanyl group together with the other three related phenylacetylenes has been synthesized and (co)polymerized by using an achiral catalytic system. Among the four monomers, only 1 is suitable to the asymmetric‐induced polymerization ( AIP ). Chiral amplification phenomenon is only observed in the copolymerization of 1 with an achiral phenylacetylene having two hydroxyl groups ( 3 ). The tight helical cis‐cisoidal main chain formed by making intramolecular hydrogen bonds between the hydroxyl groups in the copoly( 1 / 3 ) enhances the efficiency of chiral induction and as a result chiral amplification phenomenon is observed during the copolymerization.
The Lewis acid B(C6F5)3 in combination with hydrosilanes exhibits remarkable activity in the oligomerization of sulfone‐ and phosphonate‐based monomers. This process opens new routes to high‐tech silicone‐based materials, i.e., thermoplastic elastomers and heat‐resistant polysiloxanes.
A new approach for the synthesis of polyaniline (PANI) nanostructures under UV light illumination has been developed, which is the first report of a templateless chemical process for preparing pure PANI nanowires. The acceleration effect of photo‐assistance on the polymerization can promote the homogeneous nucleation and elongation of the nanofibers and nanowires, leading to easy preparation of tunable diameters of the nanowires and nanofibers of PANI.
Summary: An enzymatic one‐pot procedure has been developed for the synthesis of difunctional polyesters containing terminal thiols and acrylates. Candida antarctica lipase B was used as a catalyst for the ring‐opening polymerization of ω‐pentadecalactone. The polymerization was initiated with 6‐mercaptohexanol, then terminated with γ‐thiobutyrolactone or vinyl acrylate to create two types of difunctional polyesters with a very high content of thiol‐thiol or thiol‐acrylate end‐groups.
Summary: Nitroxide‐mediated polymerization of styrene in a continuous tubular reactor has been demonstrated for the first time. The polymerization kinetics in the tubular reactor are similar to those in a batch reactor. The number average molecular weight increases linearly with conversion, and chain extension experiments were successful, indicating that the living nature of the polymerization is maintained in the tubular reactor.
Evolution of molecular weight as measured by GPC for chain‐extended latex in continuous tubular reactor. 相似文献
Summary: Novel alternating polyketone‐based polymers bearing pendant saccharide units that are accessible by polymerization catalysis are presented. The materials were synthesized by polymerization of carbon monoxide and α‐olefins containing protected glucose or N‐acetyl glucosamine residues. The dicationic PdII bis(phoshine) complex [Pd(dppp)(NCCH3)2](BF4)2 was used as a catalyst precursor. An O‐deacetylation of the copolymers afforded materials with amphiphilic character.
Structure of the poly(1,4‐ketone) copolymers synthesized here. 相似文献
Summary: Polyaniline (PANI)/Au composite nanotubes and nanofibers are synthesized through a self‐assembly process in the presence of camphorsulfonic acid and hydrochloric acid, as dopants, respectively. The PANI/Au composites are characterized by FT‐IR, UV‐vis, and thermogravimetric analysis to verify the incorporation of the Au nanoparticles and determine the Au content. Structural characterization is performed using SEM, TEM and X‐ray diffraction. The presence of the Au nanoparticles results in an increased conductivity and improved crystallinity of the PANI. The self‐assembly method employed here is a simple and inexpensive route to synthesize multifunctional nanotubes and nanofibers and could be extended to prepare other inorganic nanoparticle/PANI composites.
The syntheses of amphiphilic block copolymers are successfully performed in water by chain extension of hydrophilic macromolecules with styrene at 80 °C. The employed strategy is a one‐pot procedure in which poly(acrylic acid), poly(methacrylic acid) or poly(methacrylic acid‐co‐poly(ethylene oxide) methyl ether methacrylate) macroRAFTs are first formed in water using 4‐cyano‐4‐thiothiopropylsulfanyl pentanoic acid (CTPPA) as a chain transfer agent. The resulting macroRAFTs are then directly used without further purification for the RAFT polymerization of styrene in water in the same reactor. This simple and straightforward strategy leads to a very good control of the resulting amphiphilic block copolymers.
Summary: Fully linear polyethylene‐based latexes have been prepared by the hydrogenation of polybuta‐1,4‐diene dispersions. The latter were synthesized via dispersion ring‐opening metathesis polymerization of cycloocta‐1,5‐diene, and hydrogenated using RuCl2(PPh3)3 as catalyst, without any further treatment. A high hydrogenation efficiency was achieved as demonstrated by different techniques including DSC, and 1H NMR and FT‐IR spectroscopy. The hydrogenation process could be carried out without detrimental effect on particle size and colloidal stability as evidenced by optical microscopy and light scattering analysis.
Optical microscopy photograph of a polybutadiene‐based dispersion after hydrogenation. No change in size is observed. 相似文献
Summary: A series of high clay content Laponite XLS/polyacrylamide (PAAm) nanocomposite hydrogels (S‐M gels) with excellent resilience, low elastic hysteresis, and ultrahigh elongation, have been successfully synthesized. Based on our results, it is concluded that the mechanical properties of nanocomposite hydrogels probably depend to a great extent on the hydrophilicity and flexibility of the macromolecules. Moreover, it is found that the transparency during the in‐situ polymerization of S‐M gels does not change, which is quite different from clay/poly(N‐isopropylacrylamide) nanocomposite hydrogels.
Formation of nanocomposite hydrogels using Clay‐S by in‐situ polymerization. 相似文献
Due to its unique electronic properties, graphene has already been identified as a promising material for future carbon based electronics. To develop graphene technology, the fabrication of a high quality P‐N junction is a great challenge. Here, we describe a general technique to grow single crystalline polyaniline (PANI) films on graphene sheets using in situ polymerization via the oxidation‐reduction of aniline monomer and graphene oxide, respectively, to fabricate a high quality P‐N junction, which shows diode‐like behavior with a remarkably low turn‐on voltage (60 mV) and high rectification ratio (1880:1) up to a voltage of 0.2 V. The origin of these superior electronic properties is the preferential growth of a highly crystalline PANI film as well as lattice matching between the d‐values [∼2.48 Å] of graphene and {120} planes of PANI.
UV‐irradiation of aqueous suspensions of amino acid‐derived amphiphilic diacetylene supramolecules promotes a process that involves initial formation of species that absorb at 640 nm followed by the generation of polymers that have longer wavelength (686 nm) absorbance. The initially formed intermediate polydiacetylenes display substantial colorimetric reversibility while the long wavelength absorbing polymers show irreversible thermochromism during heating and cooling cycles. The long wavelength absorbing polydiacetylenes, formed from amino acid‐derived amphiphilic diacetylene supramolecules, are suggested to have more planer backbone structures that allow more efficient overlap of the conjugated p‐orbitals.
A new strategy for the self‐polymerization of chromophores is investigated to develop a 2,7‐carbazole‐based nonlinear optical (NLO) conjugated polymer with an increasing conjugation length of chromophores. Elongation of the conjugation‐path length in chromophores has established engineering guidelines to enhance optical nonlinearity. Compared with the traditional synthesis of an NLO polymer, the chromophores should be well‐designed at a limited conjugation spacer, and then incorporated into a polymer matrix. In this research, the π‐conjugation spacer of chromophores extended perpendicularly to the dipole of chromophores during the polymerization process. Furthermore, this study marks the first research of integrating the π‐electrons of chromophores and conjugated polymers. These conjugated backbones promote a bulk‐polarization response, leading to large NLO coefficients.
The RAFT radical polymerization of vinyl monomers in supercritical carbon dioxide was modeled using the Predici® simulation package. The sensitivity of polymerization responses on formulation and process variables was analyzed. The simulations were carried out using kinetic and physical parameters corresponding to the polymerization of methyl methacrylate in supercritical carbon dioxide, using AIBN as initiator, at 65 °C and 200 bar, and using values of the addition and fragmentation kinetic rate constants of a “typical” RAFT agent, as reference conditions. This is the first report in the literature addressing the modeling or simulation of RAFT polymerization in supercritical carbon dioxide.
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.
While network‐like assemblies are formed by amphiphilic polyphosphazenes with poly(N‐isopropylacrylamide) and ethyl tryptophan as side groups in aqueous solution, a significant morphology transformation is observed when small molecules that exhibit hydrogen‐bonding interactions with amphiphilic copolymers are introduced during the preparation of polymeric assemblies through a dialysis procedure. Depending on copolymer composition and the content of small molecules introduced, aggregates ranging from general vesicles, high‐genus vesicles, to well‐defined nanospheres can be prepared successfully as clearly evidenced by TEM observation, which suggests this procedure should be a novel approach to prepare composite vesicles.
Porous polymeric monoliths were prepared via electron beam triggered free radical polymerization of (meth)acrylates. Post‐synthesis functionalization of these supports was accomplished via electron beam initiated free radical graft polymerization of methacryloyl‐substituted NHC precursors. The grafted precursors were converted into the corresponding copper complexes. Cu‐loadings were between 1.3 mg · g−1 and 1.5 mg · g−1. These supported catalysts were used in selected CO hydrosilylation and cyanosilylation reactions using a continuous flow setup.
Kinetic modeling is used to better understand and optimize initiators for continuous activator regeneration atom‐transfer radical polymerization (ICAR ATRP). The polymerization conditions are adjusted as a function of the ATRP catalyst reactivity for two monomers, methyl methacrylate and styrene. In order to prepare a well‐controlled ICAR ATRP process with a low catalyst amount (ppm level), a sufficiently low initial concentration of conventional radical initiator relative to the initial ATRP initiator is required. In some cases, stepwise addition of a conventional radical initiator is needed to reach high conversion. Under such conditions, the equilibrium of the activation/deactivation process for macromolecular species can be established already at low conversion.
