Search Results (5)

Macrosurfactants consisting of water-soluble poly(vinylcaprolactam) (PVCap) or poly(vinylpyrrolidone) (PVP) segments with comparatively shorter hydrophobic poly(styrene) (PS) or poly(2,3,4,5,6-pentafluorostyrene) (PPFS) segments were used as kinetic hydrate inhibitors (KHIs). These were synthesized with 2-cyanopropan-2-yl N-methyl-N-(pyridin-4-yl)dithiocarbamate switchable reversible addition–fragmentation chain transfer (RAFT) agent at 60 °C or 90 °C for 1-P(S/PFS) or 1-PVCap, respectively, followed by chain extension at 90 °C or 70 °C with PVCap or PVP, respectively. The addition of PVCap to the pure methane-water system resulted in a 53% reduction of methane consumption (comparable to PVP with 51% inhibition) during the initial growth phase. A PS-PVCap block copolymer comprised of 10 mol% PS and 90 mol% PVCap improved inhibition to 56% compared to the pure methane-water system with no KHIs. Substituting PS with a more hydrophobic PPFS segment further improved inhibition to 73%. By increasing the ratio of the hydrophobic PS- to PVCap- groups in the polymer, an increase of its inhibition potential was measured. For PPFS-PVCap, an increase of PPFS ratio from 5% to 10% decreased the methane formation rate by 6%. However, PPFS-PVCap block copolymers with more than 20 mol% PPFS were unable to dissolve in water due to increase in hydrophobicity and the attendant low critical micelle concentration (CMC). Full article

High-internal-phase emulsion-templated macroporous polymers (polyHIPEs) have attracted much interest, but their surface functionalization remains a primary concern. Thus, competitive surface functionalization via physical self-assembly of macrosurfactants was reviewed. Dendritic and diblock-copolymer macrosurfactants were tested, and the former appeared to be more topologically competitive in terms of solubility, viscosity, and versatility. In particular, hyperbranched polyethyleneimine (PEI) was transformed into dendritic PEI macrosurfactants through click-like N-alkylation with epoxy compounds. Free-standing PEI macrosurfactants were used as molecular nanocapsules for charge-selective guest encapsulation and robustly dictated the surface of a macroporous polymer through the HIPE technique, in which the macroporous polymer could act as a well-recoverable adsorbent. Metal nanoparticle-loaded PEI macrosurfactants could similarly lead to polyHIPE, whose surface was dictated by its catalytic component. Unlike conventional Pickering stabilizer, PEI macrosurfactant-based metal nanocomposite resulted in open-cellular polyHIPE, rendering the catalytic sites well accessible. The active amino groups on the polyHIPE could also be transformed into functional groups of aminopolycarboxylic acids, which could efficiently eliminate trace and heavy metal species in water. Full article

In situ surfactant-free emulsion polymerization can help avoid the utilization of harmful co-solvents and surfactants in the preparation of waterborne poly(urethane-acrylate) (WPUA) nanoemulsion, but the solid content is extremely limited, which will affect the drying rate and film-forming properties. The utilization of polymerizable macrosurfactants can overcome the above problems. However, the research on cationic polymerizable macrosurfactants is extremely scarce. In this work, cationic dimethylaminoethyl methacrylate-b-alkyl methacrylates block copolymers (PDM-b-PRMA) with terminal double bonds and different hydrophobic side chain (HSC) lengths were fabricated via catalytic chain transfer polymerization (CCTP). HSC length of PDM-b-PRMA played an important role in the phase inversion, morphology, rheological behavior of WPUA nanoemulsions, as well as the comprehensive performance of WPUA/PDM-b-PRMA films. Polymerizable PDM-b-PBMA macrosurfactant had smaller molecular weight, lower surface tension and colloidal size than the random copolymer (PDM-co-PBMA) by traditional free radical polymerization. It was easy for PDM-b-PRMA to orientedly assemble at the oil/water interface and provide better emulsifying ability when the carbon number of HSC was four. Compared with WPUA/PDM-co-PBMA, WPUA/PDM-b-PBMA had a smaller particle size, stability and better film-forming properties. This work elucidated the mechanisms of HSC length in the fabrication of cationic PDM-b-PRMA and provides a novel strategy to prepare cationic WPUA of high performance. Full article

Novel, multipurpose terpolymers based on styrene (PS), tert-butyl methacrylate (tBMA) and glycidyl methacrylate (GMA), have been synthesized via Atom Transfer Radical Polymerization (ATRP). Post-synthetic modification with 1-pyrenemethylamine (AMP) allows non-covalent functionalization of carbon nanotubes, eventually yielding a conductive nanocomposite materials capable of interacting with different Volatile Organic Compounds (VOCs) by electrical resistance variation upon exposure. Moreover, facile hydrolysis of the tBMA group yields polyelectrolytic macrosurfactants with remarkable thickening properties for promising applications in water solution, such as Enhanced Oil Recovery (EOR). Full article

Nonionic-zwitterionic diblock copolymers are designed to feature a coil-to-globule collapse transition with an upper critical solution temperature (UCST) in aqueous media, including physiological saline solution. The block copolymers that combine presumably highly biocompatible blocks are synthesized by chain extension of a poly(ethylene glycol) (PEG) macroinitiator via atom transfer radical polymerization (ATRP) of sulfobetaine and sulfabetaine methacrylates. Their thermoresponsive behavior is studied by variable temperature turbidimetry and ¹H NMR spectroscopy. While the polymers with polysulfobetaine blocks exhibit phase transitions in the physiologically interesting window of 30–50 °C only in pure aqueous solution, the polymers bearing polysulfabetaine blocks enabled phase transitions only in physiological saline solution. By copolymerizing a pair of structurally closely related sulfo- and sulfabetaine monomers, thermoresponsive behavior can be implemented in aqueous solutions of both low and high salinity. Surprisingly, the presence of the PEG blocks can affect the UCST-transitions of the polyzwitterions notably. In specific cases, this results in “schizophrenic” thermoresponsive behavior displaying simultaneously an UCST and an LCST (lower critical solution temperature) transition. Exploratory experiments on the UCST-transition triggered the encapsulation and release of various solvatochromic fluorescent dyes as model “cargos” failed, apparently due to the poor affinity even of charged organic compounds to the collapsed state of the polyzwitterions. Full article