Iranian polymer journal
Volume:21 Issue: 5, 2012

The effect of typical wood composite preservatives, ammonium pentaborate (APB), nanosize copper oxide and basic copper carbonate, on the cure characteristics of phenol formaldehyde (PF) resin in the presence of wood was evaluated by solid-state 13C nuclear magnetic resonance with cross-polarization and magic angle spinning (CP/MAS). With the introduction of APB the absorption intensity and peak area of PF resin at 129.5 ppm was reduced, and the carbons in methylene bridges shifted from 65.8 to 73.5 ppm, which were the result of hydrogen bond formation between ammonium in APB and oxygen of phenolic hydroxyl, as well as coordination bond between the boron in APB and oxygen in phenolic hydroxyl and/or unreacted hydroxymethyl. In addition, the peak area at 152.7 ppm increased with the addition of poplar powder for the overlap of cellulose, hemicellulose, and lignin chemical shifts with the active groups in PF resin. However, the connection status of critically active chemical groups of condensed polymer structure in cured PF resin such as the existence of phenolic ring, phenolic hydroxyl, methylene bridges, and hydroxymethyl linkage are unchanged. Combined with relative increase in the amount of carbon in methylene bridges from 2.42 to 2.56, drop in number of carbons of unreacted hydroxyls from 1.19 to 1.07, and the reported increase in physical and mechanical properties, the nanosize copper oxide improved the curing degree of PF. Furthermore, the similar analysis indicated that basic copper carbonate delayed the curing degree of PF.

Soapless emulsion polymerization of styrene-butyl acrylate-acrylic acid was carried out using single or combined polymerizable emulsifiers, such as hydroxypropyl methacrylate sodium sulfate (HPMAS), sodium vinyl sulfate, and vinyl alkylphenol polyether sulfates (NRS-10), in the presence of colloidal nano-SiO2 solution in order to obtain films with high degree of hardness and water-resistance. Monomer conversion, formation of coagulum, viscosity, particle size, size distribution, and surface tension of the emulsions, as well as the film properties, were determined and compared with those of an emulsion prepared with the conventional emulsifier sodium dodecyl sulfate and polyoxyethylene octylphenol ether. Emulsions prepared from a mixture of two polymerizable emulsifiers NRS-10 and HPMAS (1:1, weight ratio) have presented high monomer conversion, low coagulum, and small particle sizes. When the emulsifier level increased within a certain level, the monomer conversion increased but particles size decreased. Increased amounts of reactive emulsifiers led to low monomer conversion, large amount of coagulum and small particle sizes. With the increase of nano-SiO2 the particle sizes and the viscosity of the emulsion also increased. The introduction of reactive emulsifiers improved the water-resistance of the resulting films, and the addition of nano-SiO2 increased the hardness of the coatings. Under optimal conditions, the coatings made from emulsions produced from a combination of reactive emulsifiers such as NRS-10 and HPMAS (1:1, weight ratio) at 2 % level (based on monomer weight) exhibited remarkable hardness, adhesion force and water-resistance.

The phenolic-based composites and components are widely used because of their excellent thermal, tribological and mechanical behaviors. In the present study, phenolic resin composed of hexamine, novalac, furfural, and furfuryl alcohol has been used. The effects of two carbide nanoparticles (SiC and TiC) and two oxide nanoparticles (TiO2 and ZrO2) on the tribological properties of phenolic resin were experimentally investigated. This paper intends to identify the effects of different fillers, fraction of particles and normal load on wear rate and coefficient of friction in dry sliding wear of phenolic-based nanocomposites against hard metal. The proportions of fillers were 0.5, 1 and 2 vol% and experiments were carried out under 40, 50, 60 and 70 N loads and at 0.2 m/s speed. The fillers were mixed with phenolic resin and molded in the form of a cylinder (8.5 mm diameter × 25 mm height). The samples were cured at 135 °C with a special heating cycle. The wear tests were performed on pin-on-disk testing apparatus at ambient temperature. The composite pins were tested in dry sliding against carbon steel disk. The worn surfaces of samples have been investigated by SEM and the effects of nanometer particles showed different wear mechanisms. Observations showed that carbide particles have better enhancing effect on tribological properties of phenolic resin as compared to the oxide particles. Nanocomposites with SiC particles showed the best tribological properties among the investigated samples. The optimal content of SiC nanoparticles were 1 vol%.

Applications of conducting polymers to biosensors have recently aroused much interest. This is because these molecular electronic materials offer control of different parameters such as polymer layer thickness, electrical properties and bio-reagent loading, diversity, ease of fabrication and potentially low cost, etc. Polyaniline, poly(2-anilinoethanol) and poly(aniline-co-2-anilinoethanol) preparations are performed with electrochemical (CV) method at room temperature, in a standard three-electrode cell. Homopolymer and the copolymers of aniline and 2-anilinoethanol films were deposited from 1 M acidic aqueous media containing 0.2 M aniline, 2-anilinoethanol by voltammetric sweep between −0.1 and 1 V Ag/AgCl, at 20 mV/s−1. The sweep was stopped after 30 cycles at −0.1 V Ag/AgCl and the working electrode was covered by homopolymer and copolymer of aniline and 2-anilinoethanol. Characterizations of the products were carried out by cyclic voltammograms, UV–visible, differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) and electrochemical impedance (EIS) was employed to examine the water absorption of the synthesized polymers to be used in biosensor application. Electrochemical properties of polyaniline, poly(2-anilinoethanol) and poly(aniline-co-2-anilinoethanol) were studied and it is shown that with increased (2-anilinoethanol) content in the copolymer, its electroactivity, conductivity and resistance are reduced, though the processability and adhesion properties improve. The hydrophilicity of polymer film obtained has increased with increasing (2-anilinoethanol) content which leads to salt moving to the surface of steel.

A series of shape memory biodegradable blends from poly(lactic acid) (PLA) and poly(ethylene glycol) (PEG) were prepared by solution casting method. Ethyl cellosolve-blocked polyisocyanate (EC-bp) was synthesized and used as a cross-linker to obtain cross-linked PLA/PEG blends. The chemical structure of the prepared composite was confirmed by Fourier transform infrared spectra. Thermomechanical, thermal and shape memory properties of the blends were investigated and compared by dynamic mechanical analysis, thermogravimetric analysis and shape memory testing. The results showed that EC-bp cross-linked PLA/PEG blends had better thermal and thermomechanical properties than non-cross-linked blends and displayed good shape memory effects in both shape fixity rate and shape recovery rate. Moreover, the effect of EC-bp addition on the rate of biodegradable degradation in a phosphate buffer solution (pH 7.4) was studied at 37 °C. The prepared cross-linked PLA/PEG blends demonstrated better degradation resistance compared to the non-cross-linked blends.

Poly[5,5′-methylene-bis(2-hydroxybenzaldehyde)1,2-phenylenediimine] resin was prepared and characterized by employing elemental, thermal analysis, FTIR, and UV–visible spectroscopy. The metal uptake behavior of synthesized polymer towards Cu(II), Co(II), Ni(II), Fe(III) and Cd(II) ions was investigated and optimized with respect to pH, shaking speed, and equilibration time. The sorption data of all these metal ions followed Langmuir, Freundlich, and Dubinin–Radushkevich isotherms. The Freundlich parameters were computed 1/n = 0.31 ± 0.02, 0.3091 ± 0.02, 0.3201 ± 0.05, 0.368 ± 0.04, and 0.23 ± 0.01, A = 3.4 ± 0.03, 4.31 ± 0.02, 4.683 ± 0.01, 5.43 ± 0.03, and 2.8 ± 0.05 mmol g−1 for Cu(II), Co(II), Ni(II), Fe(III), and Cd(II) ions, respectively. The variation of sorption with temperature gives thermodynamic quantity (ΔH) in the range of 36.72–53.21 kJ/mol. Using kinetic equations (Morris–Weber and Lagergren equations), values of intraparticle transport and the first-order rate constant was computed for all the five metals ions. The sorption procedure is utilized to preconcentrate these ions prior to their determination by atomic absorption spectrometer. It was found that the adsorption capacity values for metal-ion intake followed the following order: Cd(II) > Co(II) > Fe(III) > Ni(II) > Cu(II).

Nano-sized Pd/polystyrene composite nanoparticles were prepared via surfactant-free emulsion polymerization. The as-prepared composite particles were used as a catalyst for Suzuki reaction, and they showed excellent catalytic properties in the conversion and recyclability. First, polystyrene (PS) latex particles bearing carboxyl groups on the surfaces were synthesized via one-stage surfactant-free emulsion polymerization employing acrylic acid as the functional monomer. Thus, made the PS particles negatively charged and could attract positively charged Pd2+ ions. By adding PdCl2 solution to this functional polystyrene emulsion, Pd2+ ions were attached to the surfaces and reduced to zero valent particles by the reducing agent, NaBH4. Nano-sized Pd/PS composite particles could be synthesized via this facile method. The amount of the functional monomers, the Pd2+ content and the amount of the initiator played important roles to the final morphologies of the composite particles. The resulting composite microspheres were observed by TEM. Furthermore, catalytic properties of the as-prepared Pd/PS composite particles were studied via Suzuki reaction, and the results were characterized by FTIR and 1H-NMR. The Pd/PS composite particles showed excellent conversion and could be recycled easily for reuse. After each round of Suzuki reaction, the Pd/PS composite particles could be separated just by filtration, the conversion still remained as high as 70.2 %, even when used 5 times.