Polyaniline nanostructures (nanosheets, nanofibers, and nanoparticles) can be assembled at the organic/aqueous interface or in solution by controlling the diffusion rate and the polymerization induction time of aniline. The quality of polyaniline nanostructures is determined by the polymerization solution conditions. Polyaniline nanosheets formation mechanism was proposed. Under certain polymerization conditions, polyaniline nanofibers or/and nanoparticles were obtained.
Polyethylenes and highly syndiotactic poly(propylene)s possessing chain end hydroxyl groups were synthesized by living polymerizations using L2TiCl2 [ 1 , L: C6F5NCH(2 O C6H3 3 tBu)]/MAO and functionalized α‐olefins, H2CCH(CH2)n Y [ 2 ; YOAlMe2, n = 4 ( 2a ); YOSiMe3, n = 9 ( 2b )]. Because the primary insertion of 2 to a cationic species L2Ti+ Me ( 3 ) derived from 1 /MAO is much faster than the successive secondary insertion of 2 , addition of an equimolar amount of 2 to 3 resulted in the quantitative formation of L2Ti+ CH2 CH(Me) (CH2)n Y [ 4 ; YOAlMe2, n = 4 ( 4a ); YOSiMe3, n = 9 ( 4b )]. These cationic species 4 served as functionalized initiators for the living polymerization of both ethylene and propylene and afforded polyolefins having extremely narrow molecular weight distributions and a hydroxyl group at the initiating chain end. The terminating chain end of the syndiotactic poly(propylene)s was also functionalized by adding an excess amount of 2b as a chain end capping agent to the living L2Ti–polymeryl species. Due to much slower insertion of the second molecule of 2b relative to the first one, the obtained polymers were end capped quantitatively by a single molecule of 2b . Telechelic syndiotactic poly(propylene)s were successfully synthesized through a living polymerization initiated by 4b and an end capping using 2b .
4‐Vinylbenzoyl azide was synthesized from p‐vinylbenzoic acid and polymerized by free radical polymerization. The obtained polymer contained acyl azide groups which were thermally transformed to the corresponding isocyanato groups. Reactions on these polymers with ethanol, hydroxyethyl methacrylate and 1‐pyrenebutanol proceeded quantitatively. Time‐resolved FT‐IR studies of the reactions with ethanol were carried out by varying the concentration and temperature. The effect of the solvent polarity on the Curtius rearrangement was investigated.
Langmuir‐Blodgett films of a cellulose derivative containing porphyrins, porphyrin‐cellulose, were fabricated in order to construct a cellulose‐based molecular photocurrent generation system. On visible light illumination of the LB monolayer film deposited on an ITO electrode, anodic photocurrents were observed with a quantum yield of 1.6% at an applied potential of 0 V versus SCE, and 3.8–4.6% at 0.2–0.3 V versus SCE. These values indicate that the self‐quenching of the photoexcited porphyrins in the cellulose LB film was suppressed, while porphyrin moieties in the LB film had a densely packed structure. This is because the porphyrins are located at a distance of approximately 1.0 nm along the cellulose backbone.
Gold nanoparticles are formed to cover the surface of sulfonated‐polystyrene (PS) beads by the in‐situ ion‐exchange and chemical reduction of a stable cationic gold ligand, which makes it different from the physical adsorption or multiple electroless metallization methods. PS beads are synthesized by dispersion polymerization with a diameter of 2.7 µm, and their surface is modified by introducing sulfonic acid groups (SO) to give an ion exchange capacity of up to 2.25 mequiv. · g−1, which provides 1.289 × 1010 SO per bead. Subsequently, the anionic surface of the PS beads is incorporated with a cationic gold ligand, dichlorophenanthrolinegold(III) chloride ([AuCl2(phen)]Cl), through an electrostatic interaction in the liquid phase to give gold nanoparticles (ca. 1–4 nm in diameter) formed on the PS surface. Assuming that approximately three SO groups interact with one [AuCl2(phen)]+ ion in the ion‐exchange process, the gold coverage on a PS bead is estimated as 12.0 wt.‐%, which compares well with the 16.8 wt.‐% of gold loading measured by inductively coupled plasma–mass spectrometry. Because of the adjustable IEC values of the polymer surface and the in‐situ metallization of Au in the presence of S atoms, both of which are of a soft nature, the developed methodology could provide a simple and controllable route to synthesize a robust metal coating on the polymer bead surface.
This work focused on the synthesis and aqueous self‐assembly of a series of novel hyperbranched star copolymers with a hyperbranched poly[3‐ethyl‐3‐(hydroxymethyl)oxetane] (HBPO) core and many linear poly[2‐(dimethylamino)ethyl methacrylate] (PDMAEMA) arms. The copolymers can synchronously form unimolecular micelles (around 10 nm) and large multimolecular micelles (around 100 nm) in water at room temperature. TEM measurements have provided direct evidence that the large micelles are a kind of multimicelle aggregates (MMAs) with the basic building units of unimolecular micelles. It is the first demonstration of the self‐assembly mechanism for the large multimolecular micelles generated from the solution self‐assembly of hyperbranched copolymers.
The 3‐miktoarm star‐shaped ABC copolymers of polystyrene–poly(ethylene oxide)–poly(ethoxyethyl glycidyl ether) (PS‐PEO‐PEEGE) and polystyrene–poly(ethylene oxide)–polyglycidol (PS‐PEO‐PG) with low polydispersity indices (PDI ≤ 1.12) and controlled molecular weight were synthesized by a combination of anionic polymerization with ring‐opening polymerization. The polystyryl lithium (PS−Li+) was capped by EEGE firstly to form the functionalized polystyrene (PSA) with both an active ω‐hydroxyl group and an ω′‐ethoxyethyl‐protected hydroxyl group, and then the PS‐b‐PEO block copolymers, star(PS‐PEO‐PEEGE) and star(PS‐PEO‐PG) copolymers were obtained by the ring‐opening polymerization of EO and EEGE respectively via the variation of the functional end group, and then the hydrolysis of the ethoxyethyl group on the PEEGE arm. The obtained star copolymers and intermediates were characterized by 1H NMR spectroscopy and SEC.
A new 2‐oxazoline monomer with a protected thiol group, 2‐[2‐(4‐methoxybenzylsulfanyl)ethyl]‐2‐oxazoline, MOB‐SOx , was synthesized from commercially available compounds. MOB‐SOx and 2‐ethyl‐2‐oxazoline (EtOx) were simultaneously polymerized yielding well defined copolymers with narrow molar mass distributions and target polymer chain length. The copolymerization was initiated by N‐methyl‐2‐methyl‐2‐oxazolinium triflate ( MeOxOTf ). After quantitative deprotection, poly(2‐oxazoline) with pendant thiol groups was obtained. The thiol groups were quantitatively added to the double bond of N‐phenyl‐acrylamide ( PhA ) and benzylmaleimide ( BzM ). Graft copolymers were obtained by reaction of those SH containing polymers with poly(2‐methyl‐2‐oxazoline)s bearing acrylamide ( PMeOx 10 A ) and maleimide ( PMeOx 10 M ) as terminal reactive groups.
Reversible addition–fragmentation chain transfer (RAFT) chemistry can be effectively employed to construct macromolecular architectures of varying topologies. The present article explores the principle design routes to star, block, and comb polymers in the context of theoretical design criteria for the so‐called Z‐ and R‐group approaches. The specific advantages and disadvantages of each approach are underpinned by selected examples generated in the CAMD laboratories. In particular, we demonstrate how the modeling of full molecular weight distributions can be employed to guide the synthetic effort. We further explore the theory and practice of generating amphiphilic block copolymer structures and their self‐assembly. In addition, the article foreshadows how modern synthetic techniques that combine RAFT chemistry with highly orthogonal click chemistry can be employed as a powerful tool that furthers the enhancement of macromolecular design possibilities to generate block (star) copolymers of monomers with extremely disparate reactivities. Finally, the ability of RAFT chemistry to modify the surface of well‐defined nano‐ and microspheres as devices in biomedical application is detailed.
PANI‐PAN coaxial nanofibers have been prepared by electro‐spinning during polymerization. The surface of the resulting nanofibers is superhydrophobic with a water contact angle up to 164.5°. Conductivity of the PANI‐PAN nanofibers is about 4.3 × 10−2 S · cm−1. The superhydrophobic nanofibers show a chemical dual‐responsive surface wettability, which can be easily triggered by changing pH value or redox properties of the solution. A reversible conversion between superhydrophobicity and superhydrophilicity can be performed in a short time. The strategy used here may provide an easy method to control the wettability of smart surfaces by using properties of low‐cost functional polymers.
