A new kind of binary polymer brushes was synthesized from two immiscible polymers, PMMA and PEG, on GPS‐modified silicon wafers. Surface composition, layer thickness, coverage, chain density, wetting ability, morphology and protein adsorption of the binary brushes were investigated by XPS, ellipsometry, AFM and contact angle measurements. The results show that both PMMA and PEG were successfully grafted onto the surface. The surface coverage and the chain density of PMMA and PEG brushes can be controlled by modulating the reaction temperature and time. This kind of binary polymer brushes exhibits a distinct microphase‐separated structure and excellent protein‐preventing property.
Copolymers of 3,4‐ethylenedioxythiophene and 3‐methylthiophene have been prepared by recurrent potential pulses using monomer mixtures with various concentration ratios, their properties being compared with those of the corresponding homopolymers. In addition, different technological applications have been tested for the generated copolymers. Results indicate that the properties of the copolymers are closer to those of poly(3,4‐ethylenedioxythiophene) than to those poly(3‐methylthiophene). Furthermore, the ability of the copolymers to store charge and to interact with plasmid DNA suggest that they are very promising materials.
A procedure for the production of carbon nanotube (CNT) reinforced poly(vinylidine difluoride) (PVDF) powders has been developed. These powders are versatile precursors for a range of nanocomposite materials. The morphology of the CNT/PVDF powder can be related to the interaction between filler and matrix, which depends on the degree of modification of the polymer with grafted maleic anhydride (MAH‐graft‐PVDF). The mechanical performance of the nanocomposite containing 2.5 wt.‐% CNT and 1.25 ppm of MAH increased in tensile modulus, tensile strength, and strain to failure by 34, 30, and 22%, respectively, as compared to PVDF.
A simple process is described for preparing transparent composite sheets from soy‐oil‐based biopolyurethane (BioPU) with microcrystalline cellulose (MCC). The sheets are prepared by the reaction of a mixture of soy‐oil‐based polyol and petrochemical polyol with polymeric methyldiphenyl diisocyanate (pMDI) in the presence and absence of MCC reinforcement by compression molding. MCC is well dispersed in the PU matrix, and characteristic peaks for MCC and BioPU are shown by the FTIR spectra. Mechanical properties are substantially improved with increasing MCC content. DMA and TGA results show better thermal stability in comparison to the neat BioPU sheets.
Novel materials were prepared from dual photo and thermal polymerization of hybrid thiol‐ene/cationic systems. In the first stage, the thiol‐ene system proceeded to high conversions, while the cationic photopolymerization was inhibited. The formation of sulfides during this stage was the main factor for the inhibition of the cationic photopolymerization of the epoxy monomers. Once those sulfides were formed, they reacted with the oxonium‐terminated growing polyether chains to form trialkylsulfonium salts. These salts promoted the thermal polymerization of the epoxy monomers in the second stage. The viscoelastic properties of the resulting polymers were measured by DMA.
5‐Methacrylamidopentyl ( 3a ), 10‐(N‐methylacrylamido)decyl ( 3b ), or 11‐(N‐methylacrylamido)undecyl dihydrogen phosphate ( 3c ) are synthesized by (meth)acrylation of the corresponding ω‐aminoalkane‐1‐ols with methacrylic anhydrid or acryloyl chloride followed by phosphorylation of the formed ω‐(meth)acrylamidoalkane‐1‐ols. The monomers show a significantly improved hydrolytic stability compared to the corresponding methacrylate‐based dihydrogen phosphates. The photopolymerization of 3a–c with a bis(acrylamide) crosslinker confirms a high reactivity in the free‐radical copolymerization. These monomers enable the mediation of a strong bond between the enamel or dentin surface and a restorative composite under self‐etching conditions.
A fluorinated acrylic resin was synthesized for use as a co‐monomer with a commercially available epoxy resin for UV‐cured interpenetrating polymer network preparation. Hybrid IPN networks were achieved with morphology ranging from a co‐continuous IPN to complete phase separation simply by changing monomer ratios. Highly hydrophobic coatings with good adhesion properties on glass substrates were obtained.
Orthopedic‐grade PMMA bone cement, admixed with prophylactic antibiotics, is widely used in hip and knee replacement surgery. There is a critical need to improve its structural integrity and to control antibiotic release. In this study, clay nanotubes are loaded with the antibiotic gentamicin sulfate and the cement is doped with 5–8 wt% nanotubes. The halloysite nanotubes isolate the drug from the cement monomers and serve as nanocontainers for sustained release of the antibiotic. Gentamicin‐loaded clay nanotubes admixed in PMMA cement provide sustained release up to 300–400 h and with enhanced release at cement cracks. The PMMA/halloysite/gentamicin composite tensile strength does not deteriorate as compared with pure cement and its adhesion to bone is significantly increased.
Novel nanocomposites prepared by melt mixing of MWCNTs in a hot‐melt adhesive PCL‐based polyurethane are investigated. The nucleating effect of MWCNTs and the confinement they cause to polymer chains are considered. The broadening of the glass transition is indicative of a growth of the immobilized amorphous fraction adhered to MWCNTs. In the molten state the formation of a combined polymer/MWCNT network is observed. Practical requisites of hot melt adhesives, such as adequate melting temperature, crystallization degree, and viscosity are preserved when MWCNTs are added. Improvement of strength at room temperature and welding rate during cooling, are observed.
Acrylic‐epoxy interpenetrating polymer networks were prepared by means of UV curing. The photopolymerization process was investigated via real‐time FTIR spectroscopy. The hybrid, cured films showed a broad tan δ peak in DMTA demonstrating the high damping properties of the hybrid, cured formulations. A decrease on shrinkage was achieved by increasing the epoxy‐resin content in the photocurable formulation, with a consequent increase in adhesion properties.
Bio‐based TPUs from dimer acid‐based polyols are synthesised by using a two‐step prepolymer process including reactive processing. The effect of the polyol on the final chemical structures, morphologies and properties of bio‐based TPUs is evaluated by different analytical techniques. It is observed that the percentage of hard segment (HS) distributed in organised and unorganised phases is a key factor to control the materials properties. DSC reveals that the percentages of HS dispersed in the soft domains are high at low experimental HS contents. Multiscale microscopies show better defined organised structures with increasing HS content in TPUs, highlighting the importance of the distribution between hard and soft segments in the material structure.
The depletion of selected substituted phenol stabilizers from systems simulating self‐etching dental adhesives is studied. If the adhesive monomer is an acrylate derivative, the stabilizer disappears quickly. Experimental results support the hypothesis that the phenol stabilizers are depleted from the system via a non‐radical reaction with the acrylic double bond in addition to the free‐radical mechanism. The C‐conjugate addition of aryloxide anions to the acrylate double bonds (the Michael reaction) is proposed as the reaction mechanism. The rate of the acid‐catalyzed Michael addition between acrylate monomers and phenolic stabilizers depends on the strength of the acidic catalyst.
Transparent polyimide (PI) and chemically modified graphene nanocomposite films are prepared from solutions of pyromellitic dianhydride (PMDA)/4,4′‐oxydianiline (ODA) poly(amic acid) with various amounts (0.2–0.8 wt%) of graphene carboxylic acid (GCA) in DMAc. The GCA is synthesized by modifying chemically oxidized graphene (COG) with many carboxylic acid groups (–COOH) and is well‐dispersed in DMAc, the organic solvent most frequently used for PI synthesis. The GCA sheets in the PI/GCA composite films are well‐dispersed and aligned two‐dimensionally in the direction parallel to the PI films, which enhances the mechanical properties of the nanocomposite films.
A synergistic effect of simultaneous plasticization and destructurization of soy protein in melt extrusion is studied using soy meal, glycerol, and urea. The combined effect of plasticization and destructurization yields thermoplastic soy meal (TSM) that is capable of chemical interactions with biodegradable polyesters. Melt‐compounded blends of TSM with biodegradable polyesters give new ductile bioplastics. The observed improvement in the properties of these blends might be due to two reason; the high elasticity of the destructured soy meal and the compatibility between the polyesters used. The synergistic effect of unfolding and destructurization of the protein by urea leads to high mobility in the protein chains of the soy meal.
PLLA and stereocomplexed polylactide (sc‐PLA) nanofibers were formed by electrospinning solutions of the polymers in HFIP. A highly semi‐crystalline sc‐PLA nanofiber having only sc crystallites was confirmed by WAXD analysis. The diameters of the nanofibers of both polymers decreased slightly when they were annealed at 60 °C, which was near Tg. Enzyme degradation of both as‐spun PLLA and sc‐PLA nanofibers by proteinase K from Tritirachium album was carried out. The rate of degradation of the nanofibers can be controlled by varying annealing conditions, hence the extent of crystallinity.
Low‐crystalline random and gradient P(EO‐co‐PO) copolymers and amorphous PPO and PBO of high molecular weight were synthesized by anionic coordination polymerization. Polymer gel electrolytes based on these (co)polymers were prepared and tested for long‐term performance of DSSC. The DSSC based on P(EO‐co‐PO) copolymers have longer life time compared to the homo‐PEO‐ and homo‐PPO‐based DSSC, respectively. The cells containing the chemically crosslinked copolymer gel exhibited a high efficiency of 6% after 25 d performance, whereas the solar cells based on physically crosslinked copolymer gel showed fast degradation.
The effect of nanosilica addition on the morphology and mechanical properties of blends of isotactic PP and an ethylene/octene copolymer (EOC) is studied. TEM reveals that the well‐dispersed nanoparticles are localized exclusively in the PP phase. In the presence of a maleated PP compatibilizer addition of nanosilica leads to more finely dispersed EOC domains and a finer co‐continuous morphology. The nanoparticles reduce the rate of coalescence of the dispersed phase domains. The mechanical properties depend on the EOC and PP‐g‐MA content. Tensile and flexural properties are significantly enhanced in the presence of the silica nanoparticles, whereas impact properties are not affected. These enhancements are attributed to the favorable microstructure of the blends.
Pollen has an exine shell with remarkable chemical stability, high‐strength, and unique microstructures that suggest use as a biorenewable polymer filler. Pollen‐filled polymers may offer potential for light‐weight, high‐strength materials that can displace some petroleum‐derived content with a sustainable plant‐based alternative. We report the first demonstration of the incorporation of pollen grains (short ragweed) on the mechanical, interfacial, and thermal properties of two polymers, poly(ε‐caprolactone) (PCL) and polystyrene (PS). Under certain solvent and annealing conditions, PS mechanical properties were improved synergistically upon addition of pollen, while those of PCL were always degraded, in strong agreement with wetting behavior of the polymer–pollen interface.
Polymer blend films consisting of a tacky and a nonadhesive component are promising candidates for low‐tack applications. Immiscibility of both components results in a phase separation process yielding a tacky matrix with glassy objects embedded. The influence of the blending ratio of the components poly(n‐butyl acrylate) (PnBA) and polystyrene (PS) is addressed. The mechanical information resulting from the tack test shows the possibility of varying the bonding strength of the PSA blend over a wide range. The macroscopic and microscopic structural characterization with optical microscopy and ultrasmall angle X‐ray scattering (USAXS) shows that the blend PnBA/PS exhibits similarities to common filler systems as well as deviates regarding installed structures. Due to the large domain size on a microscopic level, only the tacky component, PnBA, defines the adhesive behavior. The nonadhesive component limits the contact area between the adhesive and the substrate.
MWCNT‐based composites have been successfully synthesized via layer‐by‐layer self‐assembly of crosslinked polyphosphazene nanoparticles on the surface of MWCNTs. The amino‐terminated CNTs were characterized by XPS, FT‐IR spectroscopy, EDS, XRD and TEM. The degree of functionalization could be controlled by simply changing the mass of hexachlorocyclotriphosphazene with 4,4′‐diaminodiphenyl ether. The activity of the surface amino groups was confirmed by the reaction of these groups with HAuCl4. In addition, the effects of the mass of HCCP and ODA ratios on the content of the surface amino groups was also investigated.
