Fabrication and performance of microencapsulated phase change materials with hybrid shell by in situ polymerization in Pickering emulsion

Microencapsulated phase change materials (MePCMs) using melamine–formaldehyde resin/SiO₂ as shell were investigated in this paper. Organically modified SiO₂ particles were employed to stabilize Pickering emulsion, and in situ polymerization of melamine and formaldehyde was carried out to form hybrid shell. The performances of resultant MePCMs with hybrid shell were investigated comparatively with the MePCMs with polymer shell. SiO₂ particles raise the microencapsulation efficiency by improving the stability of emulsion and providing a precipitation site for melamine–formaldehyde resin. Also, the mechanical strength, thermal reliability, and anti‐osmosis performance of MePCMs were improved significantly by SiO₂ particles in the shell. Our study shows that Pickering emulsion is a simple and robust template for MePCMs with polymer‐inorganic hybrid shell. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of the organophosphate structure on the physical and flame‐retardant properties of an epoxy resin

2‐(6‐Oxido‐6H‐dibenzo〈c,e〉〈1,2〉oxa‐phosphorin‐6‐yl)1,4‐benzenediol (ODOPB) and bis(3‐dihydroxyphenyl) phenyl phosphate (BHPP) were successfully synthesized and used as reactive flame retardants in o‐cresol formaldehyde novolac epoxy resin. Because of the rigid, cyclic, side‐chain structure of ODOPB, the resultant phosphorus‐containing epoxy resin exhibited a higher glass‐transition temperature, better flame retardancy, higher modulus, and greater thermal stability than the regular bromine‐containing tetrabromobisphenol A epoxy resin and the linear, main‐chain, phosphorus‐containing BHPP epoxy resin. A UL‐94VO rating was achieved with a phosphorus content as low as 1.1% with ODOPB (comparable to a bromine content of 12% and a phosphorus content of 2.2% with BHPP) in the cured resins, and no fumes or toxic gas emissions were observed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 369–378, 2002     

Single‐Handed Helical Carbonaceous Nanotubes: Preparation,Optical Activity,and Applications

Carbon‐based nanomaterials have been widely studied in the past decade. Three approaches have been developed for the preparation of single‐handed helical carbonaceous nanotubes. The first approach uses the carbonization of organopolymeric nanotubes, where the organic polymers are polypyrrole, 3‐aminophenol‐formaldehyde resin, and m‐diaminobenzene‐formaldehyde resin. The second approach uses the carbonization of aromatic ring‐bridged polybissilsesquioxane followed by the removal of silica. Micropores exist within the walls of the carbonaceous nanotubes. The third approach uses the carbonization of organic compounds within silica nanotubes. This hard‐templating approach drives the formation of helical carbonaceous nanotubes containing twisted carbonaceous nanoribbons. All of these helical carbonaceous nanotubes exhibit optical activity, which is believed to originate from the chiral π‐π stacking of aromatic rings. They can be used as chirality inducers, and for lithium‐ion storage.     

Preparation of microencapsulated ammonium polyphosphate with montmorillonite‐melamine formaldehyde resin and its flame retardancy in EVM

Microencapsulated ammonium polyphosphate (MMT‐MF‐APP) with a montmorillonite‐melamine formaldehyde resin coating layer was successfully prepared by in situ polymerization. The product was characterized by Fourier‐transform infrared, X‐ray photoelectron spectroscopy, and scanning electron microscopy. Water absorption analysis showed that the microencapsulation of APP with the MMT‐MF resin leads to a decrease in the particle's water solubility. The microcapsules also exhibited better mechanical properties and higher flame retardancy in the ethylene–vinyl acetate copolymer with high vinyl acetate content (EVM) rubber compared with the common ammonium polyphosphate. Moreover, thermogravimetric analysis results showed that the EVM composites with MMT‐MF‐APP and dipentaerythritol (DPER) as flame retardants possess higher thermal stability than those with common APP and DPER as flame retardants. Copyright © 2011 John Wiley & Sons, Ltd.     

New anti‐bacterial polychelates: synthesis,characterization, and anti‐bacterial activities of thiosemicarbazide–formaldehyde resin and its polymer–metal complexes

New polymeric ligand (resin) was prepared by the condensation of thiosemicarbazides with formaldehyde in the presence of acidic medium. Thisemicarbazide–formaldehyde polymer–metal complexes were prepared with Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) in 1:2 metal:ligand molar ratio. The polymeric ligand and its polymer–metal complexes were characterized by elemental analysis, thermogravimetric analysis (TGA), FTIR, ¹³C NMR and ¹H NMR. The geometry of central metal ions was conformed by electronic (UV–vis) and EPR spectra. The antibacterial activities of all the synthesized polymers were investigated against Bacillus subtilis and Staphylococcus aureus (Gram‐positive) and Escherichia coli and Salmonella typhi (Gram‐negative). These compounds showed excellent activities against these bacteria using the shaking flask method. Copyright © 2008 John Wiley & Sons, Ltd.     

KF‐Melamine Formaldehyde Resin (KF‐MFR) as a Versatile and Efficient Heterogeneous Reagent for Aldol Condensation of Aldehydes and Ketones under Microwave Irradiation

KF‐Melamine formaldehyde resin (KF‐MFR) was demonstrated to be a highly efficient heterogenious catalyst for cross‐aldol condensation under microwave irradiation. In this synthesis, various aldehydes and ketones were condensed together in the presence of supported KF on melamine‐formaldehyde resin to afford different chalcone derivatives in good to excellent yields. KF‐MFR proved to have unique termal and chemical resistance and can be reused for many consecutive runs without remarkable loss in catalytic activity.     

Synthesis of Nanocomposites from Pd0 and a Hyper‐Cross‐Linked Functional Resin Obtained from a Conventional Gel‐Type Precursor

Hyper‐cross‐linked resins stemming from a gel‐type poly‐chloromethylated poly(styrene‐co‐divinylbenzene) resin (GT) have been investigated by a multi‐methodological approach based on elemental analysis, scanning electron microscopy, X‐ray microanalysis, and solvent absorption. The hyper‐cross‐linking of the parent resin was accomplished by Friedel–Crafts alkylation of the phenyl rings of the resins with the chloromethyl groups. This produced a permanent pore system comprising both micropores (<2.0 nm in diameter) and mesopores (2.2 nm). The chloromethyl groups that did not react in the hyper‐cross‐linking step were transformed into methylmercaptan groups and the latter were then converted into sulfonic groups by oxidation with hydrogen peroxide. By this procedure the extensive permanent porosity of the parent unsulfonated hyper‐cross‐linked polymer (HGT) was retained by the sulfonated polymer (HGTS). The final exchange capacity of HGTS was determined to be 0.36 mmol g^?1. HGTS was easily metalated with Pd^II and the subsequent reduction of the metal centers with either aqueous sodium borohydride, formaldehyde, or dihydrogen produced three Pd⁰/HGTS nanocomposites. The metal nanoparticles had diameters in the 1–6 nm range for all the nanocomposites, as determined by TEM, but with somewhat different distributions. When formaldehyde was used, more than 90 % of the nanoparticles were less than 3 nm and their radial distribution throughout the polymer beads was quite homogeneous. These findings show that with this reducing agent the metal nanoparticles are generated within the pore system of the polymer matrix, hence their size is controlled by the dimensions of the pores of the polymeric support.     

Microencapsulated ammonium polyphosphate with urea–melamine–formaldehyde shell: preparation,characterization, and its flame retardance in polypropylene

Microencapsulated ammonium polyphosphate (MCU‐APP) with urea–melamine–formaldehyde (UMF) resin is prepared by in situ polymerization, and is characterized by FTIR and XPS. The microencapsulation of APP with the UMF resin leads to a decrease in the particle's water solubility. The flame retardant actions of MCU‐APP and APP in PP are studied using limiting oxygen index (LOI) and UL‐94 test, and their thermal stability is evaluated by thermogravimetric analysis. It is found that the LOI value of the PP/MCU‐APP composite is higher than the value of the PP/APP composite. In comparison with the PP/MCU‐APP composites, the LOI values of the PP/MCU‐APP/DPER ternary composites at the same additive loading increase, and UL‐94 ratings of most ternary composites are raised to V‐0. The water‐resistant properties of the PP composites containing APP and MCU‐APP are studied. Moreover, the combustion behavior of the PP composites is investigated by the cone calorimeter. Copyright © 2008 John Wiley & Sons, Ltd.     

Utilization of waste tire rubber in hybrid plywood composite panel

The aim of this work was to use waste tire rubber (WTR) in the middle layer of hybrid plywood materials. The effects of four variable parameters, namely, WTR contents (430 and 720 g), resin contents (120 and 160 g/m²), hot pressing (single‐stage and two‐stage), and arrangements of veneer layers on the mechanical, physical, and acoustical properties, were studied. Beech (Fagus orientalis) and alder (Alnus glutinosa) veneers having 1.8‐mm thickness were used in the production of hybrid plywood panels. Rubber layers of 3‐ and 5‐mm thickness were used in the middle layer of plywood samples. To produce plywood panels, single‐stage and two‐stage hot‐pressing processes were used. Bonding of wood layers was performed using 120 and 160 g/m² urea‐formaldehyde resins, and to form the rubber layers and bond them to wood layers, methylene diisocyanate resin (150 g/m²) was used. Overall trend showed that with the increase in rubber content, the physical properties (water absorption, thickness swelling, and sound absorption) of the manufactured panels were improved, while the mechanical properties (modulus of rapture, modulus of elasticity, and impact strength) of the panels were reduced. Both physical and mechanical performances of plywood panels were improved with increase in resin content. An increase in the WTR content in plywood improved the composite's acoustical property. The production process of the wood/rubber plywood did not significantly affect their properties. The order of improvement in the physical properties of the panels is rubber content > resin content > arrangement of layers > pressing process. Copyright © 2015 John Wiley & Sons, Ltd.     

Electroinduced oxidative copolymerization of N‐vinyl carbazole with methyl ethyl ketone formaldehyde resin

In this study, a novel procedure to obtain the non‐crosslinked, photoconductive, white form of the linear copolymer of N‐vinyl carbazole (NVCz) and methyl ethyl ketone formaldehyde resin (MEKF‐R) is reported. A possible mechanism of copolymerization is suggested. The yield of the copolymer is increased almost 10 times by the addition of catalytic amounts of ceric ammonium nitrate as an oxidant during the electrochemical polymerization of NVCz in the presence of MEKF‐R in a divided electrochemical cell. Since cerium(III) is readily oxidized to cerium(IV) at the anode, the concentration of cerium(IV) remained constant and the deposition of green poly(NVCz) can be prevented. Copyright © 2004 John Wiley & Sons, Ltd.     

Thermal behaviour of hydroxymethyl compounds as models for adhesive resins

Urea–formaldehyde (UF) and phenol–formaldehyde (PF) resins are the most widely used wood adhesives. The first stage in resin manufacturing is the formation of methylol derivatives which polycondensation leads to building the tridimensional network. Understanding the behaviour of methylol compounds in curing provides useful information for developing appropriate resin structures. Thermal behaviour of N,N′-dihydroxymethylurea, 2- and 4-hydroxymethylphenols, urea and phenol as model compounds for UF, PF and phenol–urea–formaldehyde (PUF) resins was followed by TG-DTA method. The measurements were carried out by the labsys instrument Setaram at 30–450 °C in nitrogen flow. The characteristic signals for model compounds and for some reaction mixtures were measured by high resolution ¹³C NMR spectroscopy.     

Investigation of processing,thermal, and mechanical properties of a new composite matrix‐benzoxazine containing aldehyde group

A new benzoxazine aldehyde group containing monomer 3‐phenyl‐6‐formyl‐3, 4‐dihydro‐2H‐1, 3‐benzoxazine (Ald‐B) was synthesized via the Mannich reaction of formaldehyde, p‐hydroxybenzaldehyde, and aniline. The viscosities and curing behavior of the resins were studied. The results indicated that Ald‐B has an initial viscosity lower than 0.110 Pa s at 90°C and the maximum temperature of the exotherm was at 196°C. Dynamic mechanical analysis (DMA) of the copolymer of Ald‐B and methylenedianiline‐type bis‐benzoxazine (B‐BOZ) showed only one T_g of 251°C and high crosslink density in the matrix. The thermal stability of the copolymer was improved noticeably and the char yield at 800°C is 68.4%. The tensile strength and flexural strength of this resin cast are 72 and 137 MPa, respectively. Copyright © 2009 John Wiley & Sons, Ltd.     

Enhanced Formaldehyde‐Vapor Adsorption Capacity of Polymeric Amine‐Incorporated Aminosilicas

Airborne formaldehyde, which is a highly problematic volatile organic compound (VOC) pollutant, is adsorbed by polymeric amine‐incorporated silicas (aminosilicas), and the factors that affect the adsorption performance are systematically investigated. Three different types of polymeric amines 1) poly(ethyleneimine) branched (PEIBR); 2) poly(ethyleneimine) linear (PEILI); and 3) poly(allylamine) (PAA) are impregnated into two types of porous silicas [SBA‐15 and mesocellular foam (MCF) silicas] with systematic changes of the amine loadings. The adsorption results demonstrate that the adsorption capacity increases along with the amine loading until the polymeric amines completely fill the silica pores. This results in the MCF silica, which has a larger pore volume and hence can accommodate more polymeric amine before completely filling the pore, giving materials that adsorb more formaldehyde, with the largest adsorption capacity, q, of up to 5.7 mmol_HCHO g^?1 among the samples studied herein. Of the three different types of polymers, PAA, comprised of 100 % primary amines, showed the highest amine efficiency μ (mmol_HCHO/mmol_N) for capturing formaldehyde. The chemical structures of the adsorbed formaldehyde are analyzed by ¹³C cross‐polarization magic‐angle spinning (CP‐MAS) NMR, and it is demonstrated that the adsorbed formaldehyde is chemically attached to the aminosilica surface, forming hemiaminal and imine species. Because the chemical adsorption of formaldehyde forms covalent bonds, it is not desorbed from the aminosilicas below 130 °C based on temperature‐programed‐desorption (TPD) analysis. The high formaldehyde‐adsorption capacity and stability of the trapped formaldehyde on the amine surface in this study reveal the potential utility of aminosilicas as formaldehyde abatement materials.     

Adhesives and coatings based on phenolic/epoxy resins

Low molecular weight epoxy resin based on bis (4‐hydroxy phenyl) 1,1 cyclohexane was prepared and modified with various types of the prepared phenolic resins. Phenol–, cresol–, resorcinol–and salicylic acid–formaldehyde resins were used. The optimum conditions of formulation and curing process were studied to obtain modified wood adhesives characterized by high tensile shear strength values. This study indicated that the more suitable conditions are 1:2 weight ratio of phenol–or cresol–formaldehyde to epoxy resin in the presence of phthalic anhydride (20 wt%) of the resin content as a curing agent at 150°C for 80 min. Resorcinol–or salicylic acid–formaldehyde/epoxy resins formulated at 1:2 weight ratio were cured in the presence of paraformaldehyde (20 wt%) at 150°C for 60 min. The effect of the structure of phenolic resins on the tensile shear strength values of formulated resin samples, when mixed with the epoxy resins and cured under the previously mentioned optimum conditions for different times, was investigated. Metallic and glass coatings from the previous resins were also prepared and evaluated as varnishes or paints. Copyright © 1999 John Wiley & Sons, Ltd.     

Preparation and properties of novel benzoxazine and polybenzoxazine with maleimide groups

A benzoxazine compound with a maleimide group, 3‐phenyl‐3,4‐dihydro‐2H‐6‐(N‐maleimido)‐1,3‐benzoxazine (HPM‐Ba), was prepared from N‐(4‐hydroxyphenyl)maleimide, formaldehyde, and aniline. The chemical structure of HBM‐Ba was identified by FT‐IR, ¹H‐NMR, and elemental analysis. HPM‐Ba showed a melting point of 52–55 °C and good solubility in common organic solvents. HPM‐Ba showed a two‐stage process of thermal polymerization. The first stage arose from the polymerization of maleimide groups, and the second one was the ring‐opening reaction of benzoxazine groups. Fusible polymaleimides with a Tg of around 100 °C could be obtained by thermally polymerizing HPM‐Ba at 130 °C. Further polymerizing the polymaleimides at 240 °C resulted in a completely cured resin showing a Tg at 204 °C. Good thermal stability and self‐extinguishing behavior was observed with the cured polybenzoxazine resins. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5954–5963, 2004     

Curing kinetics of boron‐containing phenol–formaldehyde resin formed from paraformaldehyde

A boron‐containing phenol–formaldehyde resin (BPFR) was synthesized from boric acid, phenol, and paraformaldehyde. The curing reaction of BPFR was studied by Fourier‐transform infrared spectrometry and differential scanning calorimetry. According to the heat evolution behavior during the curing process, several influencing factors on isothermal curing reaction were evaluated. The results show that the isothermal kinetic reaction of BPFR follows autocatalytic kinetics mechanism, and kinetic parameters m, n, k₁, and k₂, were derived, respectively. In the latter reaction stage, the curing reaction becomes controlled mainly by diffusion. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 638–644, 2002     

Facile synthesis,characterization, and potential applications of two kinds of polymeric pH indicators: Phenolphthalein formaldehyde and o‐cresolphthalein formaldehyde

Two kinds of applicable polymeric pH indicators were synthesized by the reaction of phenolphthalein and o‐cresolphthalein with formaldehyde under alkaline conditions by a one‐pot method. The synthesized products were fully characterized with Fourier transform infrared, ¹H NMR, ultraviolet–visible spectroscopy, and gel permeation chromatography. The results indicated that the reaction was a typical phenol formaldehyde reaction. The dosage of formaldehyde and the reaction time were well controlled to obtain soluble polymers, instead of crosslinked products. The polymeric‐pH‐indicator‐immobilized poly(vinyl alcohol) (PVA) membranes were easily fabricated and had good long‐term stability under highly basic conditions and a fast equilibrium response. Moreover, the phenolphthalein formaldehyde immobilized PVA membrane had a linear response from pH 10.0 to 14.0, and so it has promise as a optical transducer for high pH value determinations. The o‐cresolphthalein formaldehyde immobilized PVA membrane had a nonlinear response from pH 9.0 to 13.0. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1019–1027, 2005     

Phenol‐urea‐formaldehyde cocondensed resol resins: Their synthesis,curing kinetics,and network properties

Several phenol‐urea‐formaldehyde (PUF) cocondensed resol resins were synthesized by different procedures. The curing kinetics and network properties of these PUF resins were examined by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). A kinetic study indicated that the activation energy values of PUF resins are generally higher than those of phenol‐formaldehyde (PF) resins during curing processes, but the curing rates of PUF resins are faster than those of PF resins. The pH values of PUF systems have a significant influence on the rate constants, although they affect the activation energy very slightly. Moreover, the dependence of activation energy on the conversion showed that there are more individual reactions with different activation energies occurring during the curing processes in PUF resins than in PF resins. The decomposition of methylene ether bridges to form methylene bridges probably occurs at high temperature in PUF resins. DMTA data indicated that the network rigidity of PUF resins is slightly lower than that of PF resin. The gel point and T_{tan δ2} transition measured by DMTA were consistent with the kinetic results obtained from the DSC data, but they were also related to the physical and mechanical properties of the network, especially with regard to the T_{tan δ2} transition. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1929–1938, 2003     

Fabrication of Covalently Attached Multilayer Film Electrode Containing Iron Porphyrin and Its Electrocatalysis Toward Sulfite

Construction of a highly stable covalently attached multilayer film electrode containing iron porphyrin was achieved by UV irradiation of ionic self‐assembled multilayer films of diazo‐resins (DAR) and anionic Fe(III)tetrakis(p‐sulfonatophenyl)porphyrin (FeTSPP). The multilayer films had been characterized by UV, IR spectra and cyclic valtammetry. The electrocatalytic transformation of sulfite to SO₄^2? by the multilayer film electrode containing FeTSPP was investigated. In 0.1 M NH₄OH? NH₄Cl buffer solution (pH 8.74) and 0.1 M borate buffer solution (pH 9.18) the electrocatalytic oxidation of sulfite through the multilayer film electrode can be performed. However, in acetate buffer solution (pH 4.0) the electrocatalytic reduction of sulfite by the multilayer film electrode had also good activity. The modified electrode also exhibited a fast response and good stability.     

Azide/alkyne‐“click”‐reactions on amino resin materials: An LC‐ESI‐TOF analysis

This article describes the reaction of amino resins with functional molecules using the azide/alkyne‐“click”‐reaction, opening a simple chemical modification of amino resins under aqueous conditions. Alkyne‐modified melamine‐formaldehyde resins are prepared via a direct cocondensation approach using propargylic alcohol (21.6–86.3 mmol) as additive. Subsequently, alkyne‐modified mono‐, bi‐, and trinuclear melamine‐species are identified via LC‐ESI‐TOF methods proving the covalent incorporation of alkyne‐moieties in amounts of up to 3.9 mol %. Subsequent modification of the alkyne‐modified resins was accomplished by reaction of functional azides (octyl azide (1), (azidomethyl)benzene (2), 1‐(6‐azidohexyl) thymine (3), and 4‐azido‐N‐(2,2,6,6‐tetramethylpiperidin‐4‐yl)benzamide (4)) with Cu(I)Br and DIPEA as a base. The formation of triazolyl‐modified MF‐resins was proven by LC‐ESI‐TOF methods, indicating the successful covalent modification of the amino resin with the azides 1 – 4 . © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010