Giant tubular and toroidal vesicles from self-assembled triblock copolymer-polyaniline complexes in water

An ABA type amphiphilic triblock copolymer was synthesized via ATRP and sulfonation. New self-assembled morphologies such as toroidal vesicles, giant tubular vesicles, and perforated spherical vesicles were observed from triblock copolymer-polyaniline complexes in water. The mechanism of morphology transformation at different compositions was discussed.

Water-soluble complexes of an acrylamide copolymer and ionic liquids for inhibiting shale hydration

Here, we report water-soluble complexes of an acrylamide copolymer and ionic liquids for inhibiting shale hydration. The copolymer, denoted as PAAT, was synthesised via copolymerisation of acrylamide (AM), acrylic acid (AA) and N,N-diallyl-4-methylbenzenesulfonamide (TCDAP), and the ionic liquids used were 3-methyl imidazoliumcation-based tetrafluoroborates. X-ray diffraction showed that compared with commonly used KCl, the water-soluble complex of PAAT with 2 wt% ionic liquid 1-methyl-3-H-imidazolium tetrafluoroborate (HmimBF4) could remarkably reduce the d-spacing of sodium montmorillonite in water from 19.24 to 13.16 Å and effectively inhibit clay swelling. It was also found that the PAAT-HmimBF4 complex with 2 wt% HmimBF4 could retain 75% of the shale indentation hardness and increase the anti-swelling ratio to 85%. 13C NMR revealed that there existed interactions between PAAT and HmimBF4. Moreover, the thermal stability of the PAAT-HmimBF4 complex is superior to PAAT, suggesting that this water-soluble complex can be used to inhibit clay and shale hydration in high-temperature oil and gas wells.

Graphene/tri-block copolymer composites prepared via RAFT polymerizations for dual controlled drug delivery via pH stimulation and biodegradation

A novel tri-block copolymer poly(oxopentanoate ethyl methacrylate)-block-poly(pyridyl disulfide ethyl acrylate)-block-poly(ethylene glycol acrylate) [poly(OEMA-b-PDEA-b-PEGA)], retaining active keto groups and pyridyl disulfide (PDS) side functionalities, was synthesized as a drug delivery vehicle using reversible addition-fragmentation chain transfer (RAFT) polymerization method. One mimic drug pyridine-2-thione (PT) was introduced into the monomer, PDEA for copolymerization. The other mimic drug O-benzylhydroxylamine (BHA) was conjugated with tri-block copolymer via efficient oxime coupling chemistry, followed by the attachment onto graphene via π-π stacking interaction to obtain a graphene/tri-block copolymer composite. 1H NMR, UV-vis absorption spectroscopy, fluorescence spectroscopy, gel permeation chromatography (GPC), atomic force microscope (AFM) and transmission electron microscope (TEM) were used to verify the successful step-wise preparation of the tri-block copolymer and drug loaded composite. In vitro release behaviors of BHA and PT from graphene/tri-block copolymer composite via dual drug release mechanisms were investigated. BHA can be released under acid environment, while PT will be released in the presence of reducing agents, such as dithiothreitol (DTT) or glutathione (GSH). It can be envisioned that this novel composite could be exploited as a novel intracellular drug delivery system via dual release mechanisms.

A water-soluble antimicrobial acrylamide copolymer containing sulfitobetaine for enhanced oil recovery

Herein, we report a novel acrylamide copolymer with antimicrobial property as an enhanced oil recovery chemical. The copolymer was synthesized from acrylamide (AM), acrylic acid (AA) and 2-((2-(acryloyloxy)ethyl)dimethylammonio)ethyl sulfite (ADMES) using oxidation-reduction initiation system. Subsequently, the copolymer AM/AA/ADMES was evaluated and characterized on several aspects such as IR, ¹H NMR, intrinsic viscosity, and dissolubility. The AM/AA/ADMES solution exerted remarkable thickening ability, salt tolerance ability and viscoelasticity. In addition, the rheological properties, temperature resistance ability and long-term stability of AM/AA/ADMES were investigated systematically in the presence of sulfate-reducing bacteria and relatively low viscosity loss could be obtained compared to partially hydrolyzed polyacrylamide. On the basis of core flooding experiments, AM/AA/ADMES was found to be a valuable prospect with 10.5 resistance factor, 4.6 residual resistance factor and up to 11.0% enhanced oil recovery.

Morphology and mechanical properties of nanostructured thermoset/block copolymer blends with carbon nanoparticles

Here we report the effect of multi-walled carbon nanotubes (MWCNTs) and thermally reduced graphene (TRG) on the miscibility, morphology and final properties of nanostructured epoxy resin with an amphiphilic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymer. The addition of nanoparticles did not have any influence on the miscibility of PEO-PPO-PEO copolymer in the resin. However, MWCNTs and TRG reduced the degree of crystallinity of the PEO-rich microphases in the blends above 10 wt.% of copolymer while they did not change the phase morphology at the nanoscale, where PPO spherical domains of 20-30 nm were found in all the samples studied. A synergic effect between the self-assembled nanostructure and the nanoparticles on the toughness of the cured resin was observed. In addition, the nanoparticles minimized the negative effect of the copolymer on the elastic modulus and glass transition temperature in the resin.

Synthesis and self-assembly of block copolymer/conjugated polymer complexes

 This thesis describes the procedure for preparing polymer nanoparticles of various morphologies via simple complexation technique. The nanoparticles observed in this study may find potential application in drug delivery, diagnostic imaging, nano reactors, catalysis and preparation of stimuli responsive materials.

An anti-biodegradable hydrophobic sulfonate-based acrylamide copolymer containing 2,4-dichlorophenoxy for enhanced oil recovery

We report here a novel anti-biodegradable hydrophobic acrylamide copolymer that was prepared from acrylamide, acrylic acid, sodium 3-(allyloxy)-2-hydroxypropane-1-sulfonate and N-allyl-2-(2,4-dichlorophenoxy) acetamide using the 2,2'-azobis(2-methylpropionamide) dihydrochloride initiation system. Subsequently, the copolymer was characterized by FT-IR, 1H NMR, TG-DTG and water-solubility. And the biodegradability test indicated that the copolymer was not deemed to be readily biodegradable via a closed bottle test established by the Organization for Economic Co-operation and Development (OECD 301 D). Meanwhile the copolymer could significantly enhance the viscosity of the aqueous solution in comparison with partially hydrolyzed polyacrylamide. A viscosity retention of 51.9% indicated the result of a dramatic improvement of temperature tolerance. And then the excellent salt resistance, shear resistance, viscoelasticity, long-term stability of the copolymer could be obtained, which provides a good theoretical foundation for the application in enhanced oil recovery. In addition, this copolymer exerted stronger mobility control ability with a resistance factor of 22.1 and a residual resistance factor of 5.0, and superior ability for enhanced oil recovery of 12.9%. Hence, the copolymer has potential application for enhanced oil recovery in high-temperature and high-salinity reservoirs.

A facile method to enhance ferroelectric properties in PVDF nanocomposites

Poly(vinylidene fluoride) (PVDF)/nanoclay composites were prepared using melt compounding. The effect of acrylic rubber (ACM) as a compatibilizer on different polymorph formation and on the ferroelectric properties of nanocomposites were investigated. The intercalation and morphological structure of the samples were studied using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The infrared spectroscopy and X-ray analysis revealed the coexistence of β and γ crystalline forms in PVDF-clay nanocomposite, while in partially miscible PVDF/ACM/clay hybrids, three polymorphs of α, β and γ coexisted. The coefficients of electric field-polarization (E-P) Taylor expansion were calculated based on the Lorentz theory. Using a genetic algorithm, complex dielectric susceptibilities as well as the dielectric constants for each sample were calculated and optimized. The predicted dielectric constants were found to be in good agreement with the experimental results. A dielectric constant of 16 (10 Hz) was obtained for PVDF/ACM/clay (90/10/5), which was 40% higher than that of the PVDF-clay (100/5) nanocomposite without ACM. The improved dielectric performance of the nanocomposites can be attributed to the compatibilizing effect of ACM, which facilitated the growth of β polymorph in the sample.

Crystalline polymorph transition in poly(vinylidene fluoride) (PVDF)/acrylic rubber(ACM)/clay partially miscible hybrid

This study investigates the intercalation of nanoclay in partially miscible blends of poly(vinylidene fluoride) (PVDF) and acrylic rubber(ACM). Transmission electron microscopy and X-ray diffraction technique were used to investigate the formation of nanoscale polymer blend/clay hybrids. Using Infrared spectroscopy and X-ray analysis, the different polymorph formation in PVDF nanocomposite and conjugated phases of partially miscible nanocomposite was studied. Nanoclay was found to induce β and γ polymorphs while ACM tend to induce α phase in this polymer system. It was shown that PVDF chains in ACM-rich phase of partially miscible nanocomposites interact with ACM chains which in return form α polymorph in the presence of ACM. Further observations revealed that nanoclay in α polymorph is wrapped by ACM molecules.

Hydrogen bonding interactions in poly(ε-caprolactone-dimethyl siloxane-ε-caprolactone)/poly(hydroxyether of bisphenol A) triblock copolymer/homopolymer blends and the effect on crystallization, microphase separation and self-assembly

This study investigated the self-assembled microphase separated morphologies that are obtained in bulk, by the complexation of a semicrystalline poly(ε-caprolactone-dimethyl siloxane-ε-caprolactone) (PCL-PDMS-PCL) triblock copolymer and a homopolymer, poly(hydroxyether of bisphenol A) (PH) in tetrahydrofuran (THF). In these blends, microphase separation takes place due to the disparity in intermolecular interactions; specifically, the homopolymer interacts with PCL blocks through hydrogen bonding interactions. The crystallization, microphase separation and crystalline structures of a triblock copolymer/homopolymer blends were investigated. The phase behavior of the complexes was investigated using small-angle X-ray scattering and transmission electron microscopy. At low PH concentrations, PCL interacts relatively weakly with PH, whereas in complexes containing more than 50 wt% PH, the PCL block interacts significantly with PH, leading to the formation of composition-dependent nanostructures. SAXS and TEM results indicate that the lamellar morphology of neat PCL-PDMS-PCL triblock copolymer changes into disordered structures at 40-60 wt% PH. Spherical microdomains were obtained in the order of 40-50 nm in complexes with 80 wt% PH. At this concentration, the complexes show a completely homogenous phase of PH/PCL, with phase-separated spherical PDMS domains. The formation of these nanostructures and changes in morphology depends on the strength of hydrogen bonding between PH/PCL blocks and also the phase separated PDMS blocks.

Assembled block copolymer stabilized high internal phase emulsion hydrogels for enhancing oil safety

Accidental spills and subsequent fires during oil storage and transportation periods cause serious damage to environments. Herein, we present a novel route to enhance oil safety by transforming oils into high internal phase emulsion (HIPE) hydrogels. These HIPE hydrogels are stabilized by solvent- or pH-driven assembled block copolymer (BCP), namely poly(4-vinylpyridine)-block-poly(ethylene glycol)-block-poly(4-vinylpyridine) (4VPm-EGn-4VPm). The assembled BCP shows high efficiency to stabilize HIPE hydrogels with a low concentration of 1.0 (w/v) % relative to the continuous aqueous phase. The volume fraction of the dispersed organic phase can be as high as 89% with a variety of oils, including toluene, xylene, blended vegetable oil, canola oil, gasoline, diesel, and engine oil. These smelly and flammable liquids were formed into HIPE hydrogels and thus their safety was enhanced. As the assembly is pH sensitive, oils trapped in the HIPE hydrogels can be released by simply tuning pH values of the continuous aqueous phase. The aqueous phase containing BCP can be reused to stabilize HIPE hydrogels after naturalization. These assembled BCP stabilized HIPE hydrogels offer a novel and safe approach to preserve and transport these smelly and flammable liquid oils, avoiding environmental damage.

A facile method to fabricate carbon nanostructures via the self-assembly of polyacrylonitrile/poly (methyl methacrylate-b-polyacrylonitrile) AB/B' type block copolymer/homopolymer blends

The self-assembly and high temperature behavior of AB/B′ type block copolymer/homopolymer blends containing polyacrylonitrile (PAN) polymers were studied for the first time. Here, microphase separated nanostructures were formed in the poly(methyl methacrylate-b-polyacrylonitrile) (PMMAN) block copolymer and their blends with homopolymer PAN at various blend ratios. Additionally, these nanostructures were transformed into porous carbon nanostructures by sacrificing PMMA blocks via pyrolysis. Spherical and worm like morphologies were observed in both TEM and AFM images at different compositions. The thermal and phase behavior examinations showed good compatibility between the blend components in all studied compositions. The PAN homopolymer (B′) with a comparatively higher molecular weight than the corresponding block (B) of the block copolymer is expected to exhibit ‘dry brush’ behavior in this AB/B′ type system. This study provides a basic understanding of the miscibility and phase separation in the PMMAN/PAN system, which is important in the nanostructure formation of bulk PAN based materials with the help of block copolymers to develop advanced functional materials.

Enhancement of ion dynamics in organic ionic plastic crystal/PVDF composite electrolytes prepared by co-electrospinning

Electrospun fibers are widely used in composite material design and fabrication due to their high aspect ratio, high surface area and favorable mechanical properties. In this report, novel organic ionic plastic crystal (OIPC) modified poly(vinylidene difluoride) (PVDF) composite fiber membranes were prepared by electrospinning. These composite materials are of interest for application as solid electrolytes in devices including lithium and sodium batteries. The influence of the OIPC, N-ethyl-N-methylpyrrolidinium tetrafluoroborate [C2mpyr][BF4], on the morphology and phase behavior of the composite fibers was investigated by scanning electron microscopy and Fourier transform infrared spectroscopy. Compared with pure electrospun PVDF fibers, which have an electroactive β phase and a small amount of non-polar α phase, the ion-dipole interaction between OIPC and the polymer in the co-electrospun composite system can reduce the non-polar α phase PVDF, resulting in almost entirely electroactive β phase PVDF. Differential scanning calorimetry shows that the ion-dipole interaction between the OIPC and PVDF can also interrupt the crystalline structure of the OIPC. Solid state NMR analysis also reveals different molecular dynamics of the [C2mpyr][BF4] in co-electrospun fibers compared with pure OIPC. Thus, electrospun [C2mpyr][BF4]/PVDF composite fibers that combine both increased ionic conductivity and almost pure β phase PVDF are demonstrated.

A novel α-aminophosphonic acid-modified acrylamide-based hydrophobic associating copolymer with superb water solubility for enhanced oil recovery

As a non-renewable resource, the rational exploitation of oil has attracted a large amount of attention. Among many methods for enhanced oil recovery, polymer flooding is the most suitable method of chemical flooding for non-marine reservoirs and therefore various modified acrylamide-based copolymers have been studied. In this study, a novel α-aminophosphonic acid-modified hydrophobic associating copolymer was successfully synthesized by copolymerization of acrylamide, acrylic acid, N-allyldodecanamide and 1-(dimethylamino)allylphosphonic acid. The copolymer was characterized by FT-IR, 1H NMR and thermogravimetry and exhibited superior water solubility and thickening capability. Subsequently, the shear resistance, temperature resistance and salt tolerance of the copolymer solution were investigated. The value of apparent viscosity retention of a 2000 mg L-1 copolymer solution was as high as 58.55 mPa s at a shear rate of 170 s-1 and remained at 40.20 mPa s at 120 °C. The values of apparent viscosity retention of 55.41 mPa s, 59.95 mPa s and 52.97 mPa s were observed in solutions of 10000 mg L-1 NaCl, 1200 mg L-1 MgCl2, and 1200 mg L-1 CaCl2, respectively. These were better than those of partially hydrolyzed polyacrylamide under the same conditions. In addition, an increase of up to 14.52% in the oil recovery rate compared with that for water flooding could be achieved in a core flooding test using a 2000 mg L-1 copolymer solution at 65 °C.