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
Block copolymer nanopaticles were prepared from the mixture solutions containing good/poor solvents by a simple evaporation process. The block copolymers formed disorder, unidirectionally stacked lamellar, and onion‐like structures in nanoparticles depending on preparation temperatures. Thermal annealing induced the disorder‐order phase transition and order‐order phase transformation in the block copolymer nanoparticles, even though the annealing temperature is lower than the of one polymer segment. The unusual thermal behaviors suggest that the glass transition temperature of the block copolymer is decreased by the effect of nanoparticle, whose surface areas are larger than their volumes.
Summary: A series of novel mesogen‐jacketed liquid crystal miktoarm star rod‐coil block copolymers were synthesized via atom transfer radical polymerization (ATRP). Their architectures {coil conformation of styrene segment and rigid rod conformation of {2,5‐bis[(4‐methoxyphenyl)oxycarbonyl]styrene} (MPCS) segment} were confirmed by GPC, 1H NMR, and MALDI‐TOF studies. The liquid crystalline behaviors of the synthesized copolymers are evidenced from POM observation. The liquid crystalline phase depends on the molecular weights of the rigid rod arm of miktoarm star copolymers.
This review covers the literature concerning the modification of polysaccharides through controlled radical polymerizations (NMP, ATRP and RAFT). The different routes to well‐defined polysaccharide‐based macromolecules (block and graft copolymers) and graft‐functionalized polysaccharide surfaces as well as the applications of these polysaccharide‐based hybrids are extensively discussed.
The ability of star‐shaped, block copolymer‐based unimolecular micelles to encapsulate and transport guest molecules was studied. Analytical ultracentrifugation studies clearly showed that methyl‐orange guest molecules could be encapsulated and transported, together with unimolecular micelles consisting of 5‐arm, star‐shaped block copolymers with a poly(ethylene glycol) core and a poly(ε‐caprolactone) corona. Sedimentation‐velocity and equilibrium measurements were performed to determine the sedimentation coefficients, molar masses, and diffusion coefficients of the loaded, unimolecular micelles. It was observed that the transport of guest molecules by unimolecular micelles was a function of the molecular weight of the star‐shaped block copolymers and therefore also of their size.
Summary: Amphiphilic cylindrical brush‐coil block copolymers consisting of a polystyrene coil and a cylindrical brush block with poly(acrylic acid) side chains are prepared by ATRP of t‐butylacrylate from a block comacroinitiator. Upon acidolysis of the poly(t‐butylacrylate), water‐soluble polymers were obtained that were observed to form micelles consisting of 4–5 block copolymers on average in aqueous solution. The star‐like nature of such micelles was clearly visualized by scanning force microscopy.
Schematic of coil‐cylindrical brush block copolymer PS‐b‐(PiBEMA‐g‐PAA), its AFM image clearly showing the main chain and the PAA corona of the cylindrical brush block. 相似文献
Investigations on the self‐assembly of block copolymers in solution have in some way a less well‐studied history than the study of their phase separation in the solid state, and many aspects are yet not completely understood. Here we focus on the behavior of a specific class of copolymers, namely semicrystalline block copolymers, capable of forming cylindrical aggregates in a solvent selective for the non‐crystalline, complementary block. A common model of micellization is proposed, in principle applicable to most of these copolymeric systems.
Supramolecular self‐assembly of block copolymers in aqueous solution has received ever‐increasing interest over the past few decades due to diverse biological and technological applications in drug delivery, imaging, sensing and catalysis. In addition to relative block lengths, molecular weights and solution conditions, chain architectures of block copolymers can also dramatically affect their self‐assembling properties in selective solvents. This feature article mainly focuses on recent developments in the field of supramolecular self‐assembly of amphiphilic and double hydrophilic block copolymers (DHBCs) possessing nonlinear chain topologies, including miktoarm star polymers, dendritic–linear block copolymers, cyclic block copolymers and comb‐shaped copolymer brushes.
Based on their rigid‐rod structure all‐conjugated, rod‐rod block copolymers show a preferred tendency to self‐assemble into low‐curvature vesicular or lamellar nanostructures independent from their specific chemical structure and composition. This unique and attractive behaviour is clearly illustrated in a few examples of such all‐conjugated block copolymers. The resulting nanostructured heteromaterials may find applications in electronic devices or artificial membranes.
The self‐assembly of amphiphilic diblock copolymers in block selective solvents is well documented in the scientific literature. It gives rise to micelles in which the insoluble blocks form a core, which is surrounded by a corona that contains the soluble blocks. Another method to trigger micellization consists in introducing additional non‐covalent interactions such as electrostatic interactions or hydrogen bonding in an initially soluble block copolymer. The non‐covalent complexes that result from these interactions should be insoluble in order to induce micellization. Such insoluble complexes can be generated by mixing, in a non‐selective solvent for all the individual blocks, two block copolymers or a block copolymer and a homopolymer, that contain mutually interacting blocks. This mixing process may, therefore, lead to insoluble non‐covalent complexes, which further aggregate into micellar cores stabilized by the uncomplexed blocks. Such a strategy has been successfully implemented in both aqueous and non‐aqueous solvents to create interesting stimuli‐responsive systems, mainly using ionic interactions and hydrogen bonding. This feature article will summarize these approaches.
A series of novel biodegradable random copolymers of 5‐benzyloxy‐1,3‐dioxan‐2‐one (5‐benzyloxy‐trimethylene carbonate, BTMC) and glycolide were synthesized by ring‐opening polymerization. The copolymers were characterized by nuclear magnetic resonance (NMR) spectroscopy and gel permeation chromatography (GPC). The incorporation of BTMC units into the copolymer chains results in good solubility of the polymers in common solvents. The in vitro degradation rate can be tailored by adjusting the composition of the copolymers.
The in vitro degradation of the homopolymers and poly(BTMC‐co‐GA) copolymers. 相似文献
Summary: PE‐block‐PS and P(E‐co‐P)‐block‐PS block copolymers were synthesised via sequential monomer addition during homogeneous polymerisation on various phenoxyimine catalysts. One phenoxyimine catalyst was tailored to produce high molecular weight block copolymers containing both, polyolefin and polystyrene segments. According to chromatographic analysis and TEM morphology studies, blends of block copolymers and PE homopolymers [or P(E‐co‐P), respectively] were formed. The direct olefin/styrene block copolymer synthesis on phenoxyimine catalysts represents an attractive, new one‐pot route to styrenic block copolymers which are commercially prepared by anionic styrene/diene block copolymerisation followed by hydrogenation.
The synthesis of poly(N‐vinylcarbazole)‐based block copolymers functionalized with rhenium diimine complexes or pendant terpyridine ligands is reported. The copolymers are synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization, and they exhibit interesting morphological properties as a result of the phase separation between different blocks. The rhenium complex polymer block may function as a photosensitizer, while the terpyridine‐containing polymer block can be used as the template for nanofabrication by selective deposition of zinc complexes.
Poly(2‐hydroxyethyl methacrylate)‐block‐poly(N‐isopropylacrylamide) (PHEMA‐b‐PNIPAM) was prepared by controlled surface‐initiated ATRP from silicon substrates, and the resulting block copolymers were successfully converted into the corresponding PSEMA‐b‐PNIPAM by esterification of the hydroxy groups on the PHEMA block using excess of succinic anhydride. The PSEMA‐b‐PNIPAM block copolymer brushes respond to both temperature and pH stimuli. The double‐responsive behavior of the block copolymer brushes in solution was investigated by height imaging and force–distance measurements of AFM. The results clearly show the responsive behavior of the smart block copolymer brushes.
We present a combinatorial approach to the synthesis of block copolymer series by anionic polymerization, utilizing a specially designed reactor setup. The setup features one main reactor and three secondary reactors to carry out anionic polymerizations on laboratory‐scale quantities at low temperatures. The implementation was demonstrated with three series of AB‐ and ABC‐block copolymers with identical A‐ and AB‐blocks, respectively. The B‐block in AB‐diblock copolymers and the C‐block in ABC‐triblock copolymers can be varied with respect to block length or chemical constitution. Well‐defined series of block copolymers are useful for advanced optimization of functional block copolymers in nanotechnology applications.
Well‐defined amphiphilic block‐graft copolymers PCL‐b‐[DTC‐co‐(MTC‐mPEG)] with polyethylene glycol methyl ether pendant chains were designed and synthesized. First, monohydroxyl‐terminated macroinitiators PCL‐OH were prepared. Then, ring‐opening copolymerization of 2,2‐dimethyltrimethylene carbonate (DTC) and cyclic carbonate‐terminated PEG (MTC‐mPEG) macromonomer was carried out in the presence of the macroinitiator in bulk to give the target copolymers. All the polymers were characterized by 1H NMR and gel permeation chromatography (GPC). The polymers have unimodal molecular weight distributions and moderate polydispersity indexes. The amphiphilic block‐graft copolymers self‐assemble in water forming stable micelle solutions with a narrow size distribution.
Summary: The use of the block copolymers polystyrene‐block‐poly(ethylene oxide) and poly(methyl methacrylate)‐block‐poly(ethylene oxide) is described to assist the direct solubilization of single‐walled carbon nanotubes (SWNTs) into water under ultrasonic irradiation. As compared to surfactants and homopolymers, the block copolymer systems may offer the potential of additional unique morphologies through self‐assembly. TEM and AFM analyses of solution‐cast samples indicate exfoliation and wetting of the SWNTs by the block copolymer. With increasing duration of ultrasonic irradiation, an increase in solution viscosity is initially found, which suggests that it is a convenient indicator of the progress of exfoliation of the SWNTs. With continued intense ultrasonic irradiation, the solution viscosity may decrease apparently because of damage/breakage of the SWNTs.
Schematic of the interaction of the PMMA‐b‐PEO block copolymer with the single‐walled carbon nanotubes and the specific viscosity of the system in aqueous solution as a function of sonication time: results from using an ultrasound bath (‐‐‐‐▪‐‐‐‐) or an ultrasound horn (—▴—). 相似文献
Summary: Phosphonate groups were introduced into block copolymers of styrene derivatives either as single end‐groups or as small blocks using nitroxide‐mediated radical polymerization. In order to combine the hydrophobic and hydrophilic segments, block copolymers with N,N‐dimethyl acrylamide were synthesized. After hydrolysis to phosphonic acid groups, adsorption of the polymer onto metal oxides was possible.
Conversion of the phosphonate groups by transesterification with trimethylbromosilane (TMBS), followed by hydrolysis of the silylester group. 相似文献
In this work the primary mechanical property profiles of a specific class of nano‐structured polymer/inorganic hybrid materials are characterized. By utilizing sol‐gel aluminosilicate synthesis with amphiphilic polyisoprene‐block‐poly(ethylene oxide) block copolymers as structure‐directing agents, block copolymer/aluminosilicate hybrid materials are prepared with nanometer scale hexagonally packed cylinders and lamellae of the inorganic hybrid components, as evidenced by small‐angle X‐ray scattering. Systematic thermal and dynamic mechanical analyses are performed on these hybrids as well as on the constituting components. Results reveal two transitions from the low temperature, glassy state of the hybrids into high temperature elastic plateau regions, with moduli that vary over orders of magnitude as a function of composition and morphology. The first transition can be assigned to the glass transition of the PI domains while the second is ascribed to a temperature induced softening of the organic components within the PEO/hybrid domains. The results suggest that in the present nanostructured block copolymer/aluminosilicate hybrid materials composition and morphology provide a powerful tool to tailor mechanical property profiles.
