Synthesis of Well-Defined Multi-End Functionalized Polymers via Living Anionic Polymerization

Numerous applications require specific properties at polymer surfaces that differ from the bulk, while retaining the advantageous properties of the bulk polymer. In this thesis, we describe work aimed at producing a series of multi-end functionalized polystyrene and polyisoprene additives with a wide range of molecular weights, carrying 1 to 3 fluoroalkyl groups that have been prepared by end capping the living chain ends of polymers prepared via anionic polymerization reactions. The resulting polymers have a well-defined structure with interesting surface modifying properties. We have also carried out hydrogenation of end functionalized polyisoprene to form poly(ethylene-alt-propylene) with the same functional group. The resulting polymers have been used as additives in an attempt to render the surface of polymer films hydrophobic/lipophobic and we have characterized these polymer films using static contact angle measurements with water as the main contact fluid. We have systematically studied the effect of additive molecular weight, concentration and annealing conditions on the surface properties. It has been discovered that these additives undergo rapid adsorption to a surface or interface and significantly enhance surface properties. In addition, to support the contact angles results, elastic recoil detection analysis (ERDA) and Rutherford backscattering analysis (RBS) have been carried out to acquire further quantitative evidence of surface segregation

Molecular Imprinted Polymer of Methacrylic Acid Functionalised β-Cyclodextrin for Selective Removal of 2,4-Dichlorophenol

This work describes methacrylic acid functionalized β-cyclodextrin (MAA-βCD) as a novel functional monomer in the preparation of molecular imprinted polymer (MIP MAA-βCD) for the selective removal of 2,4-dichlorophenol (2,4-DCP). The polymer was characterized using Fourier Transform Infrared (FTIR) spectroscopy, Brunauer-Emmett-Teller (BET) and Field Emission Scanning Electron Microscopy (FESEM) techniques. The influence of parameters such as solution pH, contact time, temperature and initial concentrations towards removal of 2,4-DCP using MIP MAA-βCD have been evaluated. The imprinted material shows fast kinetics and the optimum pH for removal of 2,4-DCP is pH 7. Compared with the corresponding non-imprinted polymer (NIP MAA-βCD), the MIP MAA-βCD exhibited higher adsorption capacity and outstanding selectivity towards 2,4-DCP. Freundlich isotherm best fitted the adsorption equilibrium data of MIP MAA-βCD and the kinetics followed a pseudo-second-order model. The calculated thermodynamic parameters showed that adsorption of 2,4-DCP was spontaneous and exothermic under the examined conditions

Molecular Imprinted Polymer of Methacrylic Acid Functionalised β-Cyclodextrin for Selective Removal of 2,4-Dichlorophenol

This work describes methacrylic acid functionalized β-cyclodextrin (MAA-βCD) as a novel functional monomer in the preparation of molecular imprinted polymer (MIP MAA-βCD) for the selective removal of 2,4-dichlorophenol (2,4-DCP). The polymer was characterized using Fourier Transform Infrared (FTIR) spectroscopy, Brunauer-Emmett-Teller (BET) and Field Emission Scanning Electron Microscopy (FESEM) techniques. The influence of parameters such as solution pH, contact time, temperature and initial concentrations towards removal of 2,4-DCP using MIP MAA-βCD have been evaluated. The imprinted material shows fast kinetics and the optimum pH for removal of 2,4-DCP is pH 7. Compared with the corresponding non-imprinted polymer (NIP MAA-βCD), the MIP MAA-βCD exhibited higher adsorption capacity and outstanding selectivity towards 2,4-DCP. Freundlich isotherm best fitted the adsorption equilibrium data of MIP MAA-βCD and the kinetics followed a pseudo-second-order model. The calculated thermodynamic parameters showed that adsorption of 2,4-DCP was spontaneous and exothermic under the examined conditions

Thermal and anticorrosion properties of polyurethane coatings derived from recycled polyethylene terephthalate and palm olein-based polyols

Polyols of palm olein/polyethylene terephthalate (PET) were synthesized by means of incorporating recycled PET from waste drinking bottles in different proportions into palm olein alkyd in the presence of ethylene glycol. The polyols were characterized by FTIR, and theirs hydroxyl value (OHV), acid value (AV) and viscosity were determined. The formulation of the polyurethane coating was carried out by dissolving the polyol in mixed solvent of cyclohexanone/tetrahydrofuran (THF) (4 : 1) followed by reacting 1 hydroxyl equivalent of the polyol with 1.2 equivalents of methylene diphenyldiisocyanate and 0.05% dibutyltin dilaurate (DBTDL) catalyst. The coating cured through the cross-linking reactions between hydroxyl and isocyanate groups. The formation of urethane linkages was established by FTIR spectroscopy. The set films were characterized by thermal analysis. To study their anticorrosion properties, polarization measurements and EIS in 3.5% NaCl solution were determined. The coatings displayed good thermal stability and anticorrosion properties which were supported by XRD analysis. The PU7 coating, with the highest proportion of PET (up to 15% w/w), displayed significantly improved thermal stability and anticorrosion properties. It is evident that the performance of the polyurethane (PU) coatings could be enhanced by the incorporation of PET

Synthesis and Characterization of the Inclusion Complex of β-cyclodextrin and Azomethine

Abstract: A β-cyclodextrin (β-Cyd) inclusion complex containing azomethine as a guest was prepared by kneading method with aliquot addition of ethanol. The product was characterized by Fourier Transform Infrared (FTIR) spectrometer, 1 H Nuclear Magnetic Resonance ( 1 H NMR) and Thermogravimetric Analyzer (TGA), which proves the formation of the inclusion complex where the benzyl part of azomethine has been encapsulated by the hydrophobic cavity of β-Cyd. The interaction of β-Cyd and azomethine was also analyzed by means of spectrometry by UV-Vis spectrophotometer to determine the formation constant. The formation constant was calculated by using a modified Benesi-Hildebrand equation at 25 °C. The apparent formation constant obtained was 1.29 × 10 4 L/mol. Besides that, the stoichiometry ratio was also determined to be 1:1 for the inclusion complex of β-Cyd with azomethine

Synthesis of Well-Defined Three-Arm Star-Branched Polystyrene through Arm-First Coupling Approach by Atom Transfer Radical Polymerization

Here we describe a simple route to synthesize three-arm star-branched polystyrene. Atom transfer radical polymerization technique has been utilized to yield branched polystyrene involving Williamson coupling strategy. Initially a linear polymeric chain of predetermined molecular weight has been synthesized which is further end-functionalized into a primary alkyl bromide moiety, a prime requisition for Williamson reaction. The end-functionalized polymer is then coupled using 1,1,1-tris(4-hydroxyphenyl)ethane, a trifunctional core molecule, to give well-defined triple-arm star-branched polystyrene

Novel natural rubber-based epoxy coating

The use of renewable resources in development of polymeric products is becoming more relevant in the current times, braced by the scarcity of fossil resources and threat from global warming. The manuscript describes the preparation of epoxy resin from epoxidized natural rubber (ENR) via ultraviolet (UV) treatment, followed by investigation on the film properties of the coating produced by blending the natural rubber-based epoxy resin with pentaerythritol tetrakis(3-mercaptopropionate), PETMP as the hardener. The UV treatment involved is responsible to break down the natural rubber into smaller molecular weight fractions so that it becomes more compatible with common solvents and chemicals, and at the same time improves the solubility and viscosity of the resin. The results obtained are very encouraging, with significant reduction in the molecular weight of the rubber observed after 6 hours of UV treatment, and spectroscopic characterization suggests that substantial amount of epoxide group in the ENR was effectively preserved during the treatment for subsequent reaction with PETMP. The epoxide group in the UV-degraded ENR was found to react with the –SH group of PETMP after the two were blended, applied into film, and heated at 80 °C. The properties of the coatings produced were investigated via pencil hardness test, crosshatch adhesion tape test, thermal stability test, water, and chemical resistance test. Most of the coating formulations produced film with excellent hardness, adhesion and chemical resistance. Coating B and C are among the best coating formulations, with both recorded pencil hardness grade ≥ 4H, zero film removal in the adhesion test, no film defect observed during saltwater, acid and alkaline resistance test, and reasonably good thermal stability with onset of degradation above 200 °C

SrTiO3 Nanocube-Doped Polyaniline Nanocomposites with Enhanced Photocatalytic Degradation of Methylene Blue under Visible Light

The present study highlights the facile synthesis of polyaniline (PANI)-based nanocomposites doped with SrTiO3 nanocubes synthesized via the in situ oxidative polymerization technique using ammonium persulfate (APS) as an oxidant in acidic medium for the photocatalytic degradation of methylene blue dye. Field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), X-ray diffraction (XRD), UV–Vis spectroscopy, Brunauer–Emmett–Teller analysis (BET) and Fourier transform infrared spectroscopy (FTIR) measurements were used to characterize the prepared nanocomposite photocatalysts. The photocatalytic efficiencies of the photocatalysts were examined by degrading methylene blue (MB) under visible light irradiation. The results showed that the degradation efficiency of the composite photocatalysts that were doped with SrTiO3 nanocubes was higher than that of the undoped polyaniline. In this study, the effects of the weight ratio of polyaniline to SrTiO3 on the photocatalytic activities were investigated. The results revealed that the nanocomposite P-Sr500 was found to be an optimum photocatalyst, with a 97% degradation efficiency after 90 min of irradiation under solar light