Summary: Microwave‐assisted ring‐opening polymerization of ε‐caprolactone in the presence of 1‐butyl‐3‐methylimidazolium tetrafluoroborate ionic liquid using zinc oxide as a catalyst is investigated. By adding 30 wt.‐% ionic liquid, poly(ε‐caprolactone) with a weight‐average molar mass of 28 500 g · mol−1 is obtained at 85 W for 30 min. The results indicate that the polymerization could be efficiently enhanced in the presence of ionic liquids under microwave irradiation because ionic liquids can effectively absorb microwave energy.
We report the use of a PTFE‐based microfluidic device for the encapsulation of living, therapeutically‐active cells within monodisperse alginate microspheres. We present a novel microfluidic platform and a flexible experimental method for the production of alginate microspheres. Cell lines HEK293, U‐2 OS and PC12 were separately encapsulated using this method, with minimal loss of cell viability.
Poly(dimethylsiloxane) copolymers were synthesized directly from AA/BB monomers employing a CuAAC reaction (click chemistry) in a polyaddition approach. Using organic dialkynes and oligo(siloxane)s end‐functionalized with azide moieties it was possible to obtain siloxane‐based copolymers with TPE properties by click chemistry for the first time. As seen from DSC experiments, properties were strongly dependent on the incorporated organic comonomer.
A new method to control the morphology and functionality of micelles is reported. Triblock copolymer micelles with atom transfer radical polymerization initiators at the interface are prepared in aqueous solution. After in‐situ polymerization at the interface, the structures of the interface and corona change, and micelles with PDMAEMA‐PEG comb–coil coronal chains are obtained. In aqueous solution, the pH exerts an influence on the morphology of the micelles. The coronal chains adopt different conformations at different pH values. Upon drying, the two coronal chains phase separate and form nanometer‐sized domains.
Summary: Nanostructured thermosetting materials were prepared by modification of an epoxy resin with 30 wt.‐% epoxidized polystyrene‐block‐polybutadiene copolymer (PS‐b‐PepB). The copolymer self‐assembles into a well‐defined hexagonal nanoordered structure, of around 30‐nm diameter, thus establishing its use as structure‐directing agent to generate nanostructured thermosetting materials. The study confirms pathways towards tailoring interactions between thermosetting matrices and immiscible block copolymers by using the concept of functionalization to build nanostructured polymer matrices.
Structure of diglycidyl ether of bisphenol‐A/4,4′‐methylenebis(3‐chloro 2,6‐diethylaniline) cured blend containing 30 wt.‐% PS‐b‐PepB61 block copolymer. 相似文献
Poly(3‐hexylthiophene)‐b‐poly(γ‐benzyl‐L ‐glutamate) (P3HT‐b‐PBLG) rod–rod diblock copolymer was synthesized by a ring‐opening polymerization of γ‐benzyl‐L ‐glutamate‐N‐carboxyanhydride using a benzylamine‐terminated regioregular P3HT macroinitiator. The opto‐electronic properties of the diblock copolymer have been investigated. The P3HT precursor and the P3HT‐b‐PBLG have similar UV–Vis spectra both in solution and solid state, indicating that the presence of PBLG block does not decrease the effective conjugation length of the semiconducting polythiophene segment. The copolymer displays solvatochromic behavior in THF/water mixtures. The morphology of the diblock copolymer depends upon the solvent used for film casting and annealing results in morphological changes for both films deposited from chloroform and trichlorobenzene.
We report here a facile synthesis of high performance electro‐active polymer actuator based on a sulfonated polyimide with well‐defined silver electrodes via self‐metallization. The proposed method greatly reduces fabrication time and cost, and obviates a cation exchange process required in the fabrication of ionic polymer‐metal composite actuators. Also, the self‐metallized silver electrodes exhibit outstanding metal‐polymer adhesion with high conductivity, resulting in substantially larger tip displacements compared with Nafion‐based actuators.
The quartz crystal microbalance with dissipation technique (QCM‐D) and atomic force microscopy (AFM) have been employed to study the interaction of N‐tetradecyl trimethyl ammonium bromide (TdTmAB) with polyelectrolyte multilayers containing poly(sodium 4‐styrene sulfonate) (PSS) as the polyanion and either poly(allylamine hydrochloride) (PAH) or poly(diallyl dimethyl ammonium chloride) (PDADMAC) as the polycations. The multilayers were exposed to aqueous solutions of TdTmAB. This resulted in a selective removal of PDADMAC PSS layers while layers with PAH as polycation remained stable. It is suggested that PDADMAC/PSS multilayers can be employed as strippable protecting layers.
Summary: Coexisting bicontinuous morphologies, one ordered and one disordered, are investigated in a macrophase‐separated poly(styrene‐block‐isoprene) diblock copolymer/homopolystyrene (SI/hS) blend. Two‐phase behavior is attributed to the relatively high hS/S mass ratio (0.92). According to its crystallographic signature and channel coordination as discerned from three‐dimensional (3D) images generated by transmission electron microtomography (TEMT), the ordered morphology is classified as gyroid. The 3D local and global topological characteristics of both bicontinuous morphologies as measured directly from TEMT images are reported. The disordered morphology is further compared with molecular‐field simulations to ascertain the spatial distribution of the constituent species within the blend, thereby demonstrating the utility of high‐resolution 3D imaging coupled with molecular‐level simulations.
A numerical method for simulating spinodal decomposition in ternary systems with order‐of‐magnitude differences in diffusion coefficients is presented. The method has been partially verified by molecular dynamic simulations and gives results equivalent to the standard technique when the diffusivities are equal. A two‐dimensional simulation of an asymmetric polymer/polymer/polymer system reproduces an experimentally observed bimodal distribution of dispersed‐phase particle sizes. The ripening exponent for the larger particles is near the expected value of 0.33, but that for the smaller particles is only about 0.1. The method was also used for a polymer/polymer/solvent system.
In this article, electrospinning technique has been demonstrated for the synthesis of ultra‐low dielectric constant polyimide fiber membranes. Poly(amic acid) fiber membranes have been prepared as precursor. After the treatment of thermal imidization, ultra‐low dielectric constant polyimide fibers membranes can be obtained. The morphologies and structures of precursors and products are characterized by scanning electron microscopy (SEM), Fourier transmission infrared (FTIR) spectra, and a radio frequency (RF) impedance/capacitance material analyzer. The DK of the as‐prepared polyimide membrane ranges from 1.53 to 1.56, which could be applied in the electronic packaging industry.
A new general approach for rapid performance‐screening of polymer compositions is provided. Multiple compositions are generated as one‐dimensional libraries in a microextruder with step‐ or gradient‐composition changes in 2–10 g of polymer in < 1 min. To accelerate testing, environmental stress is applied to only local regions, followed by high‐sensitivity spatially resolved characterization. We applied our methodology for weathering of arrays of polymeric compositions and provided ranking of polymer/UV absorber compositions equivalent to traditional weathering data while achieved 20 times faster.
Sampling and measurement strategies for HT analysis of combinatorial 1D polymeric libraries: (1) spectroscopic monitoring of chemical properties, (2) in‐situ monitoring of mass and viscoelastic properties, (3) scanning spectroscopic analysis, and (4) spectroscopic imaging of a coiled polymeric array. 相似文献
Binary reactive/inert antifouling polymer brushes were grafted via a two step surface initiated polymerization from printed initiator monolayer and provided robust, effective polymeric surfaces for bioattachment with distinguishably reduced non‐specific adsorption. This synthetic strategy can be harnessed to build complex binary polymeric structures on substrate surfaces and the polymer brush surfaces reported in the present paper can be widely used for versatile biological study.
In the current work we present results on the controlled/living radical copolymerization of acrylonitrile (AN) and 1,3‐butadiene (BD) via reversible addition fragmentation chain transfer (RAFT) polymerization techniques. For the first time, a solution polymerization process for the synthesis of nitrile butadiene rubber (NBR) via the use of dithioacetate and trithiocarbonate RAFT agents is described. It is demonstrated that the number average molar mass, , of the NBR can be varied between a few thousand and 60 000 g · mol−1 with polydispersities between 1.2 and 2.0 (depending on the monomer to polymer conversion). Excellent agreement between the experimentally observed and the theoretically expected molar masses is found. Detailed information on the structure of the synthesized polymers is obtained by variable analytical techniques such as infrared spectroscopy (IR), nuclear magnetic resonance (NMR) spectroscopy, differential scanning calorimetry, and electrospray ionization‐mass spectrometry (ESI‐MS).
A numerical model is presented for the optimal vulcanization of 2D extruded polar rubber with microwaves and peroxides. Magnetron power and curing time are used as the input production parameters, and the output mechanical property selected for optimization is the average tensile strength of the item. A 2D thick weather strip is analyzed to validate the model. The electric field is evaluated by means of Yee cells (FDTD approach) and suitably inserted in Fourier's heat transmission law, thus allowing point‐by‐point temperature profiles to be determined. The temperature is then used to evaluate the degree of peroxidic reticulation, and thus the final tensile strength. A so‐called alternating tangent approach based on the bisection method is finally proposed to estimate the optimal magnetron power and curing time.
A triblock amphiphilic macrocycle consisting of a macrocyclic aromatic segment, a hydrophilic oligo(ethylene oxide) branch, and a hydrophobic alkyl dendron is successfully synthesized and characterized. The resulting cyclic amphiphile is observed to self‐assemble into hollow double‐layered capsules in aqueous solution, as confirmed by dynamic light scattering and cryogenic transmission electron microscopy investigations. The capsules are able to encapsulate hydrophobic guest molecules through aromatic interactions with high stability.
Organic polymers that contain ligated metals offer a variety of unique properties which include luminescence, electro‐ and photochemistry, catalysis, charge, magnetism, and thermochromism. These organic–inorganic hybrid materials have the potential to offer novel active matrixes for advanced devices. Continued progress in synthetic chemistry and molecular characterization will enable such advanced materials. Here the focus is restricted to side‐chain metal complexes with emissive properties that highlight the use of lanthanide ions as opposed to the often‐studied transition metal complexes.
Summary: This paper presents the structural influence of the Si H functionality on the physicochemical properties of polysilanes. New low‐temperature restructuring processes were discovered using thermal analysis (TGA, DSC). Photoluminescent (FL) and X‐ray photoelectron spectroscopy (XPS) measurements revealed the optoelectronic properties‐chemical structure relationship of the synthesized polymers.
Highly reactive Si H groups lead to restructuring of the main polysilane chain. 相似文献
