This paper highlights the powerful combination of reversible addition–fragmentation chain transfer (RAFT) radical polymerization and various click/coupling chemistries. This is not an exhaustive review but rather an overview demonstrating the impressive possibilities that the “marriage” of these two synthetic approaches offers in modern macromolecular design and synthesis.
Summary: The end coupling of living PSLi chains in hydrocarbon media by the addition of monoalkylbromides has been examined. A very selective PS–PS coupling reaction was obtained with neo‐pentylbromide (94%) at a ratio of PSLi/alkylbromide equal to 1 while the secondary and tertiary bromine derivatives yield only very limited coupling. The coupling mechanism is likely to involve a lithium‐bromine interchange at the PS chain end, generating polystyryl‐bromide which then reacts selectively with the remaining polystyryllithium chains.
End group modification of polymers prepared by reversible addition–fragmentation chain transfer (RAFT) polymerization was accomplished by conversion of trithiocarbonate into reactive functions able to conjugate easily with biomolecules or bioactive functionality. Polymers were prepared by RAFT, and subsequent aminolysis led to sulfhydryl‐terminated polymers that reacted in situ with an excess of dithiopyridyl disulfide to yield pyridyl disulfide‐terminated macromolecules or in the presence of ene to yield functional polymers. In the first route, the pyridyl disulfide end groups allowed coupling with oligonucleotide and peptide. The second approach exploited thiol–ene chemistry to couple polymers and model compounds such as carbohydrate and biotin with high yield.
Highly efficient formation of poly(propylene carbonate) can be achieved in the coupling of CO2 and propylene oxide assisted by 4‐(N,N‐dimethylamino)pyridine (DMAP) and catalyzed with salen chromium(III) chloride by using DMAP/Cr ratios of less than 2. Under these conditions a possible backbiting mechanism is suppressed, leading to only minor amounts of cyclic carbonate as a side product.
Nanoparticles in a flexible polymer melt film often segregate to the substrate due to attractive depletion interactions between the nanoparticles and the substrate. Here, molecular dynamics simulations are performed to study the effect of chain stiffness on this segregation. The nanoparticles are modeled as spheres and the polymers as semi‐flexible bead‐spring chains. Both purely repulsive and attractive forces are considered, while assuming non‐selective interactions among all species. The nanoparticles are found to be well‐dispersed in the system having repulsive forces only and aggregate into clusters in the completely attractive system. For the repulsive system, adding chain stiffness substantially decreases the nanoparticles' segregation, and hence their concentration, at the substrate.
The synthesis of hyperbranched poly(ethylene glycol) (hbPEG) in one step was realized by random copolymerization of ethylene oxide and glycidol, leading to a biocompatible, amorphous material with multiple hydroxyl functionalities. A series of copolymers with moderate polydispersity ( < 1.8) was obtained with varying glycidol content (3–40 mol‐%) and molecular weights up to 49 800 g mol−1. The randomly branched structure of the copolymers was confirmed by 1H and 13C NMR spectroscopy and thermal analysis (differential scanning calorimetry). MTS assay demonstrated low cell toxicity of the hyperbranched PEG, comparable to the highly established linear PEG.
Summary: Radical copolymerization of 1,1‐bis(ethoxycarbonyl)‐2‐vinylcyclopropane (ECVCP) with allyl carbonates that contain isopropyl groups yields highly branched polyvinylcyclopropanes. The polymerizations were carried out in the presence of 2,2‐azoisobutyronitrile at 150 °C in chlorobenzene. Structural analysis of the polymers suggested that radical ring‐opening polymerization proceeded through 1,5‐ring‐opening followed by transfer to the allylic carbonate comonomers. Intra‐molecular cyclization, which yields polycyclobutane units, was also observed during the polymerization.
Synthesis of branched 1,1‐bis(ethoxycarbonyl)‐2‐vinylcyclopropane by transfer to the isopropoxy functional allyl carbonate comonomers. 相似文献
An isotropic melt of a chiral side‐chain polymethacrylate was studied by electric birefringence technique. A phase transition between two different isotropic phases was detected by Kerr effect and confirmed by WAXS measurements. The obtained experimental data can explain the previously reported bistable phase behavior of the polymer, as conventional Sm A phase is formed in slow cooling whereas a TGB‐like, optically isotropic mesophase in fast cooling.
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.
Synthesis of a water‐soluble polydiacetylene has been achieved by topochemical polymerization in the solid state of the bis(N‐methylimidazolium)diacetylene monomer. Structural characterization for the monomer by X‐ray diffraction and NMR spectroscopy supports a photopolymerization initiated at the surface. Characterization of the polymer (NMR, UV and Raman spectroscopy, and dynamic light scattering) is given along with a molecular modelling interpretation of the polymerization in the solid state.
Summary: Polypyrrole nanotubes with high electric conductivity and azo function have been fabricated in high yield via an in‐situ polymerization. During the process fibrillar complex of FeCl3 and methyl orange (MO), acting as a reactive self‐degraded template, directed the growth of polypyrrole on its surface and promoted the assembly into hollow nanotubular structures.
TEM image of uncompleted PPy nanotubes synthesized in MO solutions after reaction for 40 min. 相似文献
The Michael reaction of chitosan with acrylic acid was carried out successfully, even in water alone as the reaction medium. As a consequence of its good solubility in water, the reaction product, N‐carboxyethylchitosan, showed excellent biodegradable properties with standard activated sludge.
Summary: A new strategy was developed to prepare disorderly exfoliated nanocomposites, in which a soft siloxane surfactant with a weight‐average molecular weight ( ) of 1 900 was adopted to modify the clay. The modified clay slurry was then mixed with silicone rubber by hand, and exfoliation was achieved. The proposed mechanism thereof was verified by TEM and XRD. The physical entanglement of the soft siloxane surfactant plays a vital role in the diffusion and intercalation of the matrix molecules during the compounding of the slurry‐polymer mixture. This simple method is applicable to other silicone‐based materials reinforced by clay.
TEM micrograph of silicone rubber/clay‐sil nanocomposite. 相似文献
Summary: A superhydrophobic coating was facilely fabricated in one step by casting bisphenol A polycarbonate (PC) solution under moisture. Vapor‐induced phase separation occurred during the solidifying process and a rough surface with a micro‐nano‐binary structure (MNBS) similar to the microstructure shown on lotus leaf was formed.
