Toughening of aromatic diamine-cured epoxy resins by modification with hybrid modifiers composed of N-phenylmaleimide–styrene copolymers and N-phenylmaleimide–styrene–p-hydroxystyrene terpolymers

Hybrid modifiers composed of N-phenylmaleimide–styrene copolymers (PMS), and N-phenylmaleimide–styrene–p-hydroxystyrene terpolymers (PMSH) containing pendent p-hydroxyphenyl groups as functionalities, were used to improve the toughness of bisphenol-A diglycidyl ether epoxy resin cured with p,p′-diaminodiphenyl sulphone. The hybrid modifiers were effective in toughening the epoxy resin. When using the modifier composed of 10 wt% PMS (M?_w 313000) and 2.5 wt% PMSH (2.5 mol% p-hydroxystyrene units, M?_w 316000), the fracture toughness (K_IC) for the modified resins increased 100% with no deterioration in the flexural properties and the glass transition temperature. The improvement in toughness of the epoxy resins was attained because of the co-continuous phase structure and the improvement in interfacial adhesion. The toughening mechanism is discussed in terms of the morphological characteristics of the modified epoxy resin systems.     

Poly(p-tert-butoxycarbonyloxystyrene): a convenient precursor to p-hydroxystyrene resins

An efficient synthetic route to pure, high molecular weight poly(p-hydroxystyrene) is reported. The route involves synthesis of a new monomer, p-tert-butoxycarbonyloxystyrene, polymerization by radical initiation or by cationic initiation in liquid SO₂, followed by thermolysis or acidolysis of the tert-butoxycarbonyl protecting group. Porous, crosslinked resin beads containing the nucleophilic, phenol pendant group have been prepared in a similar fashion from the precursor terpolymer of p-tert-butoxycarbonyloxystyrene, styrene and divinylbenzene. The utility of this resin for solid-phase synthesis has been demonstrated.     

Anticorrosive properties of epoxy resin coatings cured by aniline/p‐phenylenediamine copolymer

Aniline/p‐phenylenediamine copolymer [poly(ANI‐co‐p‐PDA)] was prepared by chemical oxidative polymerization. FTIR and ¹H‐NMR analysis indicate that the poly(ANI‐co‐p‐PDA) is oligomer with end‐capped amino groups, which can cure epoxy resin. The anticorrosion performance of carbon steel (CS) samples coated by epoxy resin coating cured with poly(ANI‐co‐p‐PDA) and epoxy resin coating cured with triethylenetetramine exposed to 5 wt % NaCl and 0.1 mol/L HCl aqueous solution is studied by the potentiodynamic polarization and electrochemical impedance spectroscopy. The results show that the CS coated by epoxy resin coating cured with poly (ANI‐co‐p‐PDA) has more excellent corrosion protection than that of epoxy resin coating cured with triethylenetetramine. Raman spectroscopy analysis indicates that the surface of CS coated by epoxy resin coating cured with poly(ANI‐co‐p‐PDA) forms passive layer, which is composed of α‐Fe₂O₃. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Novel biocidal polymers based on branched and linear poly(hydroxystyrene)

New biocidal polymers based on branched as well as linear poly(p-hydroxystyrene) were synthesized. Biocidal polymers were synthesized in two steps by creation of active centers via chloroacetylation of linear and branched poly(p-hydroxystyrene) using chloroacetyl chloride. The second step involves the immobilization of onium salts onto the chloroacetylated polymers. All the prepared polymers were characterized using elemental microanalysis, FT-IR, ¹H NMR spectra, and TGA. Antimicrobial activity of the prepared polymers was tested against various pathogenic microorganisms. The antimicrobial activity was found to be affected by the active group and the tested microorganism. The phosphonium salts showed higher activity than ammonium salts.     

Modification of Acid Anhydride-cured Epoxy Resins By N-Phenyl- maleimide–Styrene Copolymers and N-Phenylmaleimide–Styrene– p-Hydroxystyrene Terpolymers

N-Phenylmaleimide–styrene copolymers (PMS) and reactive N-phenylmaleimide–styrene–p-hydroxystyrene (HSt) terpolymers (PMSH) containing p-hydroxyphenyl groups were used to improve the toughness of bisphenol A diglycidyl ether epoxy resin cured with methyl hexahydrophthalic anhydride. PMS and PMSH were effective modifiers for epoxies. The morphologies of the modified resins depended on modifier structure and content. The most effective modification for the cured resins was attained because of the co-continuous structure of the modified resins in both PMS and PMSH modification systems. When using 15wt% of PMS (M¯_w 125000), the fracture toughness, K_IC, for the modified resin increased by 230%, with retention of flexural modulus and glass transition temperature, but with a loss of flexural strength, compared with the values for the unmodified epoxy resin. When using PMSH as the reactive modifier, the efficiency decreased with increase in HSt content, because of the increasing extent of dispersion of the PMSH-rich continuous phases. In the modification with 10wt% PMSH (1·0mol% HSt unit, M¯_w 294000), the modified resin had balanced physical properties. © of SCI.     

Enhancement of polystyrene composites by hyper-branched polymer-grafted nano-SiO2

Hyper-branched poly(styrene) (HPS) made from copolymerisation of styrene (St) and a branching monomer divinylbenzene (DVB) in the presence of a chain transfer agent n-dodecanethiol (C₁₂SH) was grafted onto the surface of nano-SiO₂ via emulsion polymerisation (donated as HPS-SiO₂). A series of PS/HPS-SiO₂ composites were obtained by the addition of prepared HPS-SiO₂ into the pure PS. The structures and properties of the product were characterised by Fourier-transform infrared spectra (FT-IR), differential scanning calorimetry, thermogravimetric analysis and dynamic mechanical analysis (DMA). The results showed a strong interface interaction between HPS and nano-SiO₂ indicating that the HPS has grafted onto the surface of nano-SiO₂. The storage modulus, Young’s modulus, glass transition temperature (T_g) and thermal decomposition temperature of the composite were increased apparently by loading an appropriate amount of HPS-grafted SiO_2.     

Surface modification of TiO2 nanoparticles with silane coupling agent for nanocomposite with poly(butyl acrylate)

Abstract

In order to enhance the compatibility of TiO₂ nanoparticles in poly(butyl acrylate) (PBA) matrix, surface modification of TiO₂ was conducted using 3-methacryloxypropyl-trimethoxysilane (MPS). To improve the effect of surface modification, TiO₂ was predispersed in ethanol via ultrasonic waves. The process was investigated in detail to obtain the optimum condition of ultrasonic dispersion. The dispersion of TiO₂ in ethanol was evaluated via sedimentation rate. Fourier transform infrared spectroscopy and thermogravimetric analysis were performed to investigate the effect of surface modification. It was found that the organic functional groups of MPS had been successfully grafted onto the surface of TiO₂ nanoparticles. Finally, both neat PBA film and TiO₂/PBA composite film were prepared and characterised. The modified TiO₂ presented good compatibility in PBA matrix.     

Promotion effect of molybdate support on Bi2Mo3O12 catalyst in the selective oxidation of propylene

Catalytic behavior of Bi₂Mo₃O₁₂ supported on CoMoO₄ or CO_11/12Fe_1/12MoO _x was investigated in the oxidation of propylene to acrolein. A drastic promotion effect was observed only in the catalyst supported on Co_11/12Fe_1/12MoO _x . but not on CoMoO₄. Promotion effect of cobalt and iron in the multicomponent bismuth molybdate catalyst, Mo-Bi-M^II-M^III-O was discussed.     

Thermal degradation of polymers. XVI. Thermal analysis studies on poly(p-methoxystyrene) and poly(p-hydroxystyrene) in air and nitrogen

Comparative thermal degradation studies have been made in air and nitrogen on polystyrene (PS), poly(p-methoxystyrene) (PMS), poly(p-hydroxystyrene) (PHS) and p-hydroxystyrene/styrene copolymers (p-HS/S) by thermal analytical methods (TG and DSC). The degradation behavior shown by these polymers in an oxidizing or inert atmosphere is different. PMS and PS, however, degrade in a similar manner in the same test atmosphere, suggesting that similar degradation mechanisms are operative for these systems. Polymers containing p-HS behave differently to PMS and PS in both atmospheres. Their behavior in air is discussed it terms of the antioxidant effect of the phenolic hydroxyl grouping and the related crosslinking reactions. In nitrogen, the anomalous behavior is discussed in terms of the observed carbonization reaction.     

Preparation of poly(acrylamide) grafted onto crosslinked poly (HEMA-MMA-EGDMA) beads for the removal of phenol

ABSTRACT

Poly(acrylamide) (PAAM) was grafted onto crosslinked poly(hydroxy ethyl methacrylate) (HEMA)-based beads for the removal of phenol from aqueous solution. A beaded polymer with a PAAM surface shell was prepared in two steps: synthesis of crosslinked poly (HEMA (50% mol) - MMA (40% mol) - EGDMA (10% mol)) terpolymers spherical beads (200–420 µm) (resin 1) via the suspension polymerization method; and the grafting of PAAM was carried out by redox initiation from hydroxyl groups on resin1 by using cerium (IV) ammonium nitrate as the initiator.

The resulting polymeric sorbent (resin 2) with about 82 wt.% grafted PAAM has been demonstrated to be efficient to remove phenol from water. Moreover, phenol sorption capacities of resin 1 and resin 2 were compared and sorption experiments were performed depending on the initial phenol concentration and pH. Kinetic measurements and models were studied for resin 1 and resin 2.     

Combustion of Methane at Low Temperature over Pd and Pt Catalysts Supported on Al2O3, SnO2 and Al2O3-Grafted SnO2

Pd and Pt catalysts supported on alumina, tin(IV) oxide and tin(IV) oxide grafted on alumina were prepared, characterised and tested with respect to the low-temperature combustion of methane after reduction in H₂ and ageing under reactants at 600°C. In the case of Pd, the use of SnO₂ or SnO₂-based supports led to catalysts slightly less active than Pd/Al₂O₃. In contrast, SnO₂ was found to strongly promote the oxidation of methane over Pt catalysts with respect to Pt/Al₂O₃, even after ageing under reactants. When Pt was supported on SnO₂ grafted on Al₂O₃, the activity was found at most similar to or, after ageing, lower than Pt/Al₂O₃. This negative effect was discussed, being partly related to the sintering of SnO₂ under reactants observed by FTIR and XRD.     

Alumina-supported Mn(II), Co(II), Ni(II) and Cu(II) N,N-bis(salicylidene)-2,2-dimethylpropane-1,3-diamine complexes: Synthesis, characterization and catalytic oxidation of cyclohexene with tert-butylhydroperoxide and hydrogen peroxide

New square-planar manganese(II), copper(II), nickel(II) and cobalt(II) complexes of a tetradentate Schiff-base ligand “N,N-bis(salicylidene)-2,2-dimethylpropane-1,3-diamine, H₂[salpnMe₂]” have been prepared and characterized by elemental analyses, IR, UV–Vis, conductometric and magnetic measurements. The results suggest that the symmetrical Schiff-base is a bivalent anion with tetradentate N₂O₂ donors derived from the phenolic oxygen and azomethine nitrogen. The formulae was found to be [M(salpnMe₂)] for the 1:1 non-electrolytic complexes. Alumina-supported metal complexes (ASMC; [M(salpnMe₂)/Al₂O₃]) catalyze the oxidation of cyclohexene with tert-buthylhydroperoxide (TBHP) and hydrogen peroxide. Oxidation of cyclohexene with TBHP gave 2-cyclohexene-1-one, 2-cyclohexene-1-ol and 1-(tert-butylperoxy)-2-cyclohexene whereas, oxidation with H₂O₂ resulted in the formation of cyclohexene oxide and cyclohexene-1,2-diol. Manganese(II) complex supported on alumina “[Mn(salpnMe₂]–Al₂O₃” shows significantly higher catalytic activity than other catalysts.     

Cobalt Alleviates GA-Induced Programmed Cell Death in Wheat Aleurone Layers via the Regulation of H2O2 Production and Heme Oxygenase-1 Expression

Heme oxygenase-1 (HO-1) and hydrogen peroxide (H₂O₂) are key signaling molecules that are produced in response to various environmental stimuli. Here, we demonstrate that cobalt is able to delay gibberellic acid (GA)-induced programmed cell death (PCD) in wheat aleurone layers. A similar response was observed when samples were pretreated with carbon monoxide (CO) or bilirubin (BR), two end-products of HO catalysis. We further observed that increased HO-1 expression played a role in the cobalt-induced alleviation of PCD. The application of HO-1-specific inhibitor, zinc protoporphyrin-IX (ZnPPIX), substantially prevented the increases of HO-1 activity and the alleviation of PCD triggered by cobalt. The stimulation of HO-1 expression, and alleviation of PCD might be caused by the initial H₂O₂ production induced by cobalt. qRT-PCR and enzymatic assays revealed that cobalt-induced gene expression and the corresponding activities of superoxide dismutase (SOD), catalase (CAT) and ascorbate peroxidase (APX), three enzymes that metabolize reactive oxygen species, were consistent with the H₂O₂ accumulation during GA treatment. These cobalt responses were differentially blocked by co-treatment with ZnPPIX. We therefore suggest that HO-1 functions in the cobalt-triggered alleviation of PCD in wheat aleurone layers, which is also dependent on the enhancement of the activities of antioxidant enzymes.     

Thermal degradation of polymers. XV. Vacuum pyrolysis studies on poly(p-methoxystyrene) and poly(p-hydroxystyrene)

The monomers p-hydroxystyrene (p-HS) and p-methoxystyrene (p-MS) have been synthesized and polymerized using azobisisobutyronitrile as free-radical initiator. The polymerization behavior of p-HS is anomalous, and a mechanism is suggested to account for this phenomenon. Poly(p-hydroxystyrene) (PHS) and poly(p-methoxystyrene) (PMS) homopolymers have been subjected to vacuum pyrolysis at temperatures in the range of 300–500°C. The products of degradation have been identified and qualitatively and quantitatively analyzed and the degradation behavior of the two systems compared with polystyrene. PHS shows anomalous behavior resulting from the high reactivity of the p-HS monomer and the facility for transfer afforded by the proton of the hydroxyl substituent. Mechanisms to account for the degradation behavior of each system are discussed.     

Novel amphiphilic carbon black composite nanoparticles from TEMPO-terminated polymer and TEMPO-terminated block copolymer grafted carbon black

The purpose of this study was to modify the surface characteristics of CB so as to prevent the aggregation of CB to provide the dispersibilities in either H₂O or organic solvent. In this study, five kinds of hydrophilic TEMPO-terminated polymer, hydrophobic TEMPO-terminated polymer and amphiphilic TEMPO-terminated block copolymer were synthesized. The five kinds of TEMPO-terminated polymers were: (1) poly(4-acetoxystyrene) (PAS-T), (2) poly(4-hydroxystyrene) (PHS-T), (3) polystyrene (PS-T), (4) poly(4-acetoxystyrene)-block-polystyrene (PAS-b-PS-T), (5) poly(4-hydroxystyrene)-block-polystyrene (PHS-b-PS-T). These TEMPO-terminated polymers with desired molecular weights and specific structures were synthesized by using the method of living radical polymerization in the presence of 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO). These TEMPO-terminated polymers and TEMPO-terminated block copolymers were grafted onto the surface of CB through a reaction of polymer radicals trapped by CB, so as to obtain the TEMPO-terminated polymer/CB and TEMPO-terminated block copolymer/CB composite nanoparticles. Various variables such as reaction time, reaction temperature, amount of TEMPO-terminated polymer, molecular weight of TEMPO-terminated polymer and amount of CB all of which influenced the grafting efficiency were investigated. Besides, the stability of the composite nanoparticles, which dispersed in H₂O or organic solvent, was investigated by laser light scattering. The amphiphilic composite nanoparticles, PHS-T/CB and PHS-b-PS-T/CB, which dispersed well in both H₂O and organic solvent, were synthesized successfully in this work.     

Synthesis and characterization of poly(hydroxamic acid) chelating resin from poly(methyl acrylate)‐grafted sago starch

A new chelating ion‐exchange resin containing the hydroxamic acid functional group was synthesized from poly(methyl acrylate) (PMA)‐grafted sago starch. The PMA grafted copolymer was obtained by a free‐radical initiating process in which ceric ammonium nitrate was used as an initiator. Conversion of the ester groups of the PMA‐grafted copolymer into hydroxamic acid was carried out by treatment of an ester with hydroxylamine in an alkaline solution. The characterization of the poly(hydroxamic acid) chelating resin was performed by FTIR spectroscopy, TG, and DSC analyses. The hydroxamic acid functional group was identified by infrared spectroscopy. The chelating behavior of the prepared resin toward some metal ions was investigated using a batch technique. The binding capacities of copper, iron, chromium, and nickel were excellent and the copper capacity was maximum (3.46 mmol g⁻¹) at pH 6. The rate of exchange of the copper ion was very fast that is, t_1/2 < 5 min. It was also observed that the metal ion‐sorption capacities of the resin were pH‐dependent and its selectivity toward the metal ions used is in the following order: Cu²⁺ > Fe³⁺ > Cr³⁺ > Ni²⁺ > Co²⁺ > Zn²⁺ > Cd²⁺ > As³⁺ > Pb²⁺. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1256–1264, 2001     

Methoxy poly (ethylene glycol) methacrylate-TiO2/poly (methyl methacrylate) nanocomposite: an efficient membrane for gas separation

Polymer/nanoparticle mixed matrix membranes (MMMs) is one of the most important topics in gas separation field. In this study, to improve gas separation efficiency, methoxy poly(ethylene glycol) methacrylate (MPEG) was grafted on TiO₂ surface and was used for synthesis of poly (methyl methacrylate) (PMMA) MMMs. Gas permeation and separation properties of PMMA/PMPEG-TiO₂ MMMs were studied for CO₂, CH₄, O₂, and N₂ gases. The results showed that the MMM filled with 5 wt% PMPEG-TiO₂ nanoparticle exhibited optimal separation performance with CO₂ permeability of 32.48 Barrer and CO₂/N₂ selectivity of 56.98, which are higher than pure polymer (2.75 Barrer and 36.71).     

Molecular motions and transitions in a poly(p-hydroxystyrene) derivative

The dielectric relaxation mechanisms in a poly(p-hydroxystyrene) derivative have been studied by Thermally Stimulated Depolarization Currents (TSDC) in the temperature range between −160 and 130°C. A broad relaxation was observed at low temperatures, from −160 up to 0°C, which obeyed to the zero entropy approximation. In contrast, the glass transition relaxation showed the usual behavior, a strong departure to the zero entropy prediction. Both relaxations have been studied in detail by the technique of thermal sampling. The thermal behavior of this poly(p-hydroxystyrene) derivative was also studied by Differential Scanning Calorimetry in the temperature range between 20 and 200°C. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1921–1926, 1999     

Synthesis of new electromagnetic nanocomposite based on modified Fe3O4 nanoparticles with enhanced magnetic,conductive, and catalytic properties

A new method for the fabrication of an electromagnetic nanocomposite based on Fe₃O₄ and polyaniline (PANI) is offered. The authors focused on improvement of the physical and electromagnetic properties of the nanocomposite using a new synthetic method. Supermagnetic Fe₃O₄ nanoparticles were synthesized through coprecipitation method. As a chemical modification, the third generation of poly (amidoamine) dendrimer was grafted on the surface of the nanoparticles. PANI was grafted from –NH₂ functional groups of dendrimer via in situ polymerization of aniline. Finally, Au nanoparticles were loaded on the nanocomposite and its catalytic activity for reduction reactions was studied.     

Methane activation by NO2 on Co loaded SBA-15 catalysts: The effect of mesopores (length, diameter) on the catalytic activity

In a general model of “three-function deNO_x” catalyst, the partial oxidation of methane by NO₂ is an important step (CH₄ + NO₂ → C_xH_yO_z + NO). To study the effect of the length and diameter, in the mesopores of SBA-15, we have synthesized catalysts with 3 wt.% cobalt supported on SBA-15, with differences in length and diameter of channels. Three different cobalt species were detected on all catalysts. We demonstrated by TPSR experiments that the activity of cobalt/SBA-15 catalysts is affected by the length, the diameter and connections between mesopores of the SBA-15 supports. We show that by changing textural properties of silica support the temperature of 100% conversion of NO₂ into NO can decrease by more than 100 °C.