Grass fiber reinforced phenol formaldehyde resin composite: preparation,characterization and evaluation of properties of composite

There is a growing interest in the development of new materials through utilization of natural resources. This paper describes evaluation of water leached and alkali treated chopped grass fiber reinforced phenol formaldehyde composite. Here alkali treatment of grass fiber was carried out by varying the concentration of sodium hydroxide. The thermal stability of the composite was assessed by thermogravimetric analysis (TGA). Fourier transformation infrared spectroscopic study of both water leached and alkali treated grass fiber‐phenolic resin composite was also performed. Water absorption and swelling behavior of grass fiber phenolic resin composites in water were studied and the alkali treated grass fiber‐resin composite showed less water absorption and swelling. A composite prepared from 1% alkali treated grass fiber and 55% resin, showed the highest tensile strength whereas a composite prepared from 5% alkali treated grass fiber and 55% resin, showed maximum flexural properties. Copyright © 2006 John Wiley & Sons, Ltd.     

Surface modification of glass beads with poly(acrylic acid)

Non‐porous P₂ glass beads were etched with sodium hydroxide to increase the number of silanol groups that could be used to modify the surface. The etched glass beads were then functionalized with 3‐aminopropyltriethoxysilane (APS) and/or glycidoxypropyltrimethoxysilane (GPS). The surface of the glass beads were further modified with poly(acrylic acid) (PAA) by reacting the carboxyl groups on PAA with the amino groups of the pregrafted APS. The chemical modifications were characterized by FT‐IR spectroscopy, particle size analyzer and tensiometry for contact angle and porosity measurements. Five different molecular weight PAA polymers ranging from 2000 to 3,000,000 were grafted with less than expected increase of grafted PAA with molecular weight. The amount of APS and PAA on the surface was determined from thermogravimetric analysis and elemental analysis data. The surface properties of the surface modified glass beads were determined by measuring water and hexane penetration rate and contact angle. The surface morphology was examined by scanning electron microscopy. Copyright © 2006 John Wiley & Sons, Ltd.     

Physicochemical characterization of α‐chitin, β‐chitin,and γ‐chitin separated from natural resources

We isolated α‐chitin, β‐chitin, and γ‐chitin from natural resources by a chemical method to investigate the crystalline structure of chitin. Its characteristics were identified with Fourier transform infrared (FTIR) and solid‐state cross‐polarization/magic‐angle‐spinning (CP–MAS) ¹³C NMR spectrophotometers. The average molecular weights of α‐chitin, β‐chitin, and γ‐chitin, calculated with the relative viscosity, were about 701, 612, and 524 kDa, respectively. In the FTIR spectra, α‐chitin, β‐chitin, and γ‐chitin showed a doublet, a singlet, and a semidoublet at the amide I band, respectively. The solid‐state CP–MAS ¹³C NMR spectra revealed that α‐chitin was sharply resolved around 73 and 75 ppm and that β‐chitin had a singlet around 74 ppm. For γ‐chitin, two signals appeared around 73 and 75 ppm. From the X‐ray diffraction results, α‐chitin was observed to have four crystalline reflections at 9.6, 19.6, 21.1, and 23.7 by the crystalline structure. Also, β‐chitin was observed to have two crystalline reflections at 9.1 and 20.3 by the crystalline structure. γ‐Chitin, having an antiparallel and parallel structure, was similar in its X‐ray diffraction patterns to α‐chitin. The exothermic peaks of α‐chitin, β‐chitin, and γ‐chitin appeared at 330, 230, and 310, respectively. The thermal decomposition activation energies of α‐chitin, β‐chitin, and γ‐chitin, calculated by thermogravimetric analysis, were 60.56, 58.16, and 59.26 kJ mol^?1, respectively. With the Arrhenius law, ln β was plotted against the reciprocal of the maximum decomposition temperature as a straight line; there was a large slope for large activation energies and a small slope for small activation energies. α‐Chitin with high activation energies was very temperature‐sensitive; β‐Chitin with low activation energies was relatively temperature‐insensitive. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3423–3432, 2004     

Polymerization of methyl methacrylate by 2‐pyrrolidinone and n‐dodecyl mercaptan

The bulk polymerization of methyl methacrylate initiated with 2‐pyrrolidinone and n‐dodecyl mercaptan (R‐SH) has been explored. This polymerization system showed “living” characteristics; for example, the molecular weight of the resulting polymers increased with reaction time by gel permeation chromatographic analysis. Also, the polymer was characterized by Fourier transform infrared spectroscopy, ¹H NMR, and ¹³C NMR techniques. The polymer end with the iniferter structures was found. By the initial‐rate method, the polymerization rate depended on [2‐pyrrolidinone]^1.0 and [R‐SH]⁰. Combining the structure analysis and the polymerization‐rate expression, a possible mechanism was proposed. n‐Dodecyl mercaptan served dual roles—as a catalyst at low conversion and as a chain‐transfer agent at high conversion. Finally, the thermal properties were studied, and the glass‐transition temperature and thermal‐degradation temperature were, respectively, 25 and 80–100 °C higher than that of the azobisisobutyronitrile system. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3692–3702, 2002     

Synthesis and characterization of new segmented polyurethanes with side‐chain,liquid‐crystalline chain extenders

Liquid‐crystalline, segmented polyurethanes with methoxy–biphenyl mesogens pendant on the chain extender were synthesized by the conventional prepolymer technique and esterification reaction. Two, side‐chain, liquid‐crystalline (SCLC) polyurethanes with mesogens having spacers of six and eight methylene units were prepared. The structures of the mesogenic units and SCLC polyurethanes were confirmed by Fourier transform infrared spectroscopy and ¹H NMR. Polymer properties were also examined by solubility tests, water uptakes, and inherent viscosity measurements. Differential scanning calorimetry studies indicated that the transition temperature of the isotropic to the liquid‐crystalline phase decreased with increasing spacer length. Wide‐angle X‐ray diffraction (WAXD) studies revealed the existence of liquid‐crystalline phases for both SCLC polyurethanes. Polarized optical microscopic investigations further confirmed the thermotropic liquid‐crystalline behaviors and nematic mesophases of both samples. Thermogravimetric analysis displayed better thermal stabilities for both SCLC polymers and indicated that the presence of mesogenic side chains may increase the thermal stability of segmented polyurethanes. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 290–302, 2004     

Thermal degradation of poly(acrylic acid) containing metal nitrates and the formation of YBa2Cu3O7−x

The use of polymers containing metal salts as ceramic high‐temperature superconductor (HTSC) precursors may provide a relatively simple and rapid method for producing materials that can take advantage of advanced polymer processing and then be pyrolyzed to HTSCs. The mechanisms of thermal degradation in these precursors, which have not been characterized, can be used to optimize the pyrolysis conditions for HTSC production. This article describes the degradation of a precursor based on poly(acrylic acid) (PAAc) containing yttrium, barium, and copper nitrates in the proportions needed for the formation of the HTSC YBa₂Cu₃O_7?x (YBCO). This article also describes the effects of the pyrolysis process on the resulting materials. The degradation of the precursor is a complex, multistage process. The presence of the metal ions and HNO₃ reduces the thermal stability of PAAc and increases the degradation rate. The results indicate that the initial stages of the pyrolysis should be conducted in argon or nitrogen to inhibit BaCO₃ formation and that the final stages should be conducted in air/oxygen to enhance oxidation. Optimization of the pyrolysis conditions produces a YBCO film with minimal contamination. © 2005 Wiley Periodicals, Inc. J PolymSci Part B: Polym Phys 43: 1168–1176, 2005     

Synthesis and characterization of high nitrile content polyimides as dielectric films for electrical energy storage

Three new isomeric diamines containing three, oxy‐linked benzonitriles (3BCN), one of which is asymmetric (meta, para, or m, p), are synthesized in a 3‐step sequence. Polycondensation of these diamines and four common dianhydrides (6FDA, OPDA, BTDA, and PMDA) in N,N‐dimethylacetamide via poly(amic acid) precursors and thermal curing at temperatures up to 300 °C lead to three series of tough, creasable polyimide (PI) films (tensile moduli = 1.63 ? 2.86 GPa). Among these PIs, two PMDA‐based PIs possess relatively high crystallinity and two OPDA‐based PIs, low crystallinity, whereas all 6FDA‐ and BTDA‐based PIs, and m,m‐3BCN‐OPDA‐PI are amorphous, readily soluble in common polar aprotic solvents. Thermally stable and having high T_g (216 ? 341 °C), these PIs lose 5% weight around 493–503 °C in air and 463–492 °C in nitrogen. Dielectric properties have been evaluated by broadband dielectric spectroscopy (BDS) and electric displacement‐electric‐field (D‐E) loop measurements. D‐E loop results show an increase in high temperature permittivity (at 190 °C/1 kHz) from 2.9 (for parent PI CP2 with no nitrile group) to as high as 4.9 for these PIs, while keeping their dielectric loss relatively low. Thus, an increase in dipole moment density by the presence of three neighboring CN per repeat unit can increase the overall permittivity, which could be further enhanced by sub‐T_g mobility of para‐phenylene linkages (BDS results). Published 2014. J. Polym. Sci., Part A: Polym. Chem. 2014 J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 422–436     

Synthesis,characterization, and influence of synthesis parameters on particle sizes of a new microgel family

Poly(p‐nitrophenylacrylate‐co‐methacrylamide) and poly(p‐Nitrophenylacrylate‐co‐N,N′‐isopropylacrylamide) reactive microgels were synthesized by precipitation polymerization. The process was followed qualitatively by infrared spectroscopy (ATR‐FTIR) and microgels composition was determined by nuclear magnetic resonance (¹H NMR). Scanning electron microscopy of obtained colloidal particles showed strictly spherical morphologies with a moderate polydispersity. The average hydrodynamic particle diameter and particle size distributions were measured by quasi‐elastic light scattering and the particle size distributions obtained ranged from 100 to 600 nm. Several synthetic parameters affect the particle size of these materials and thus, indirectly, their properties and future applications. In this article, we report the influence of different polymerization reaction conditions in the final microgel dimensions. For example, we observed that the different solvent‐comonomer affinity induced a significant change in swollen particle size of the copolymeric microgels. On the other hand, the crosslinking density limited the particle sizes, but an excess of crosslinker content in the reaction mixture resulted in the opposite effect. Finally, we also studied the influence of initiator content in the mean particle size. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3833–3842, 2007     

New polysaccharide-g-polyacrylonitrile copolymers: synthesis and thermal characterization

Various natural and modified polysaccharides (i.e. arabic gum, tragacanth gum, xanthan gum, sodium alginate, chitosan, sodium carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose) were modified using ceric-initiated graft polymerization of acrylonitrile under inert atmosphere. Grafting was confirmed using spectral (FT-IR) proofs. The grafting parameters were determined by conventional methods. Thermal characteristics of the homopolymer-free copolymers were studied using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) under nitrogen atmosphere. The major thermal transitions as well as the activation energy of the major decomposition stages were investigated. The polyacrylonitrile (PAN)-grafted polysaccharides were recognized to be thermally stable more than the corresponding non-grafted substrates, although they begin to decompose at relatively lower temperatures than the non-grafted counterparts. Copyright © 2003 John Wiley & Sons, Ltd.     

肌肉醇取代苯甲酸盐的合成及生物活性

本文以硫脲和硫酸二甲酯为原料反应生成S-甲基异硫脲硫酸盐,再与2-甲基氨基乙醇反应生成肌肉醇硫酸盐,分离出肌肉醇碱,最后与具有生物活性的取代苯甲酸反应生成了7种肌肉醇取代苯甲酸盐。化合物结构经IR,1H NMR和元素分析进行表征,初步室内生测结果表明该类化合物具有一定的抑菌活性。     

Ionic networks derived from the protonation of dendritic amines with carboxylic acid end‐functionalized PEGs

The synthesis and characterization of novel ionic networks linked by the ammonium salts of poly(propylene imine) (PPI) dendrimers of the first (PPI G1) and second (PPI G2) generation and two short bis carboxymethyl ether terminated poly(ethylene glycol)s (DiCOOH‐PEG) with different molecular weights (M_n ～ 250 and M_n ～ 600) are reported. Likewise, an ionic network based on PPI G1 and a long αω‐dicarboxylic acid functionalized PEG (M_n ～ 4800) were evaluated. Simpler ionic structures based on tris(2‐aminoethyl)amine or hexamethylene diamine and the short DiCOOH‐PEGs are also investigated. The ionic structures formed were confirmed by differential scanning calorimetry, Fourier Transform Infrared spectroscopy in the attenuated‐total‐reflection mode, and ¹H‐¹³C NMR spectroscopy. A comprehensive ¹H NMR analysis revealed that only the primary amines of the PPI G1 dendrimer residing at the periphery take part in the ionic network formation. In the case of PPI G2, the picture is less clear. A thorough investigation of the thermal degradation of the utilized precursors and all the ionic materials prepared was additionally performed by thermogravimetric analysis. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Two new CdII and ZnII coordination polymers incorporating 1‐aminobenzene‐3,4,5‐tricarboxylic acid: synthesis,crystal structure and characterization

Aminobenzoic acid derivatives are widely used in the preparation of new coordination polymers since they contain O‐atom donors, as well as N‐atom donors, and have a rich variety of coordination modes which can lead to polymers with intriguing structures and interesting properties. Two new coordination polymers incorporating 1‐aminobenzene‐3,4,5‐tricarboxylic acid (H₃abtc), namely, poly[(μ₃‐1‐amino‐5‐carboxybenzene‐3,4‐dicarboxylato)diaquacadmium(II)], [Cd(C₉H₅NO₆)(H₂O)₂]_n, (I), and poly[[bis(μ₅‐1‐aminobenzene‐3,4,5‐tricarboxylato)triaquatrizinc(II)] dihydrate], {[Zn₃(C₉H₄NO₆)₂(H₂O)₃]·2H₂O}_n, (II), have been prepared and structurally characterized by single‐crystal X‐ray diffraction. In polymer (I), each tridentate 1‐amino‐5‐carboxybenzene‐3,4‐dicarboxylate (Habtc^2?) ligand coordinates to three Cd^II ions to form a two‐dimensional network structure, in which all of the Cd^II ions and Habtc^2? ligands are equivalent, respectively. Polymer (II) also exhibits a two‐dimensional network structure, in which three crystallographically independent Zn^II ions are bridged by two crystallographically independent pentadentate 1‐aminobenzene‐3,4,5‐tricarboxylate (abtc^3?) ligands. This indicates that changing the metal ion can influence the coordination mode of the H₃abtc‐derived ligand and further influence the detailed architecture of the polymer. Moreover, the IR spectra, thermogravimetric analyses and fluorescence properties were investigated.     

Thermochemically induced binding of methyl orange to polycations containing primary amine groups

The thermochemical transformation of electrostatically formed complexes of methyl orange (MO) with polycations containing primary amine groups such as ammonium salts afforded new polymers with a high concentration of covalently bound 4‐N,N‐dimethylaminoazobenzene groups in the side chain. Poly(allylamine hydrochloride) and poly(β‐aminoethylene acrylamide hydrochloride) were employed as support polycations for MO. The transformation of sulfonate–ammonium ion pairs into sulfonamide bonds, via heating at an elevated temperature, was supported by the polymer properties before and after the thermal treatment. The polymer structure changes were monitored with elemental analysis, Fourier transform infrared, ¹H NMR, and ultraviolet–visible absorption spectroscopy, and thermogravimetric analysis. The spacer length between the backbone and azobenzene structures used as side chains strongly influenced the polymer properties before and after the heat‐induced reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5898–5908, 2006     

Spectral and thermal characterization of polyaniline–oxalic acid salt

Polyaniline–oxalic acid salts were prepared at 5 and 30°C by chemical polymerization of aniline using different concentration of oxalic acid. Polyaniline base was obtained from the corresponding polyaniline salt by dedoping using aqueous ammonium hydroxide solution. Conductivity measurements, elemental analysis, Infrared, electronic absorption, electron paramagnetic resonance spectral, and thermogravimetric analysis were performed on the polyaniline salts and bases. Composition and the extent of dopant in polyaniline salt systems where determined. The value of composition of polyaniline: oxalic acid is 4: 1.6 and the polymer yield is around 66%. The value of conductivity, polymer yield and composition of polyaniline–oxalic acid salt is independent of concentration of oxalic acid used and also the synthesis temperature. The results are compared with polyaniline–hydrochloride salt prepared by chemical polymerization. The conductivity of polyaniline–oxalic acid salt is three orders of magnitude lower than that of polyaniline-hydrocholoride salt. © 1995 John Wiley & Sons, Inc.     

Design,syntheses, and characterization of new thermoplastic polyureas based on 3,4‐ethylenedioxythiophene

New thermoplastic polyureas labeled PUn (n = 2, 3, 4, 6, 7, 9, or 10), based on 3,4‐ethylenedioxythiophene (EDOT) with flexible aliphatic spacers, were synthesized and characterized for the first time. EDOT was chosen as a replacement for the aromatic phenyl group in conventional thermoplastics based on urea linkages to improve solubility without compromising the thermal properties. As synthesized, all the samples exhibited a semicrystalline nature. The glass‐transition and melting temperatures showed a strong dependence on the spacer length. A comparison of the thermal properties of these polyureas with the corresponding phenyl analogues indicated that EDOT was a viable heteroatomic analogue of the phenyl group to be inserted into the main‐chain polyureas without hampering their thermal stability. The polyureas with spacer lengths greater than hexamethylene formed transparent gels in N‐methylpyrrolidone, 1,1,2,2‐tetrachloroethane, and dimethyl sulfoxide. The molecular packing of the polyureas was assigned with wide‐angle X‐ray diffraction studies. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5823–5830, 2005     

The chemistry,properties, and characterization of organotin(IV) complexes of 2-(N-naphthylamido)benzoic acid

2-(N-naphthylamido)benzoic acid was synthesized by the reaction of phthalic anhydride with naphthylamine in glacial acetic acid at room temperature. Complexes 1–9 were synthesized under reflux in good yield with general formula R_{4? n} SnL _n (R = Me, n-Bu, Ph, n-Oct, Bz and n = 2, 3), which were studied by microanalysis, IR, NMR (¹H, ¹³C, ¹¹⁹Sn), and mass spectrometry. Cytotoxicity of the synthesized compounds was checked against Brine-shrimp larvae. In vitro activities against some Gram-positive and Gram-negative bacteria and fungi were also determined. Antimicrobial activities show that species with tetrahedral geometry in solution are more toxic.     

Rose‐Like Microstructures of Polyaniline by Using a Simplified Template‐Free Method under a High Relative Humidity

3‐D rose‐like microstructures of polyaniline (PANI), which are self‐assembled from 2‐D nanosheets consisted of 1‐D nanofibers, were synthesized by a template‐free method in the presence of ammonium peroxydisulfate (APS) as both oxidant and dopant under a high relative humidity of 80% for the first time. When the relative humidity increases from 25 to 80%, not only morphology of the micro/nanostructured PANI undergoes a change from 1‐D nanofibers to 2‐D nanosheets to 3‐D rose‐like microstructures, but also increase in crystallinity. It is proposed that a cooperation effect of the oriented water molecules at the vapor–water interface and difference in hydrogen bonding energies between the interface and the bulk induced by the relative high humidity results in the formation of the 3‐D rose‐like microstructures self‐assembled from 2‐D nanosheets. Moreover, the method reported may provide a simple approach for understanding self‐assembly of complex micro/nanostructures of PANI.

     

An effective method for the synthesis of carboxylic esters and lactones using substituted benzoic anhydrides with Lewis acid catalysts

An efficient mixed-anhydride method for the synthesis of carboxylic esters and lactones using benzoic anhydride having electron withdrawing substituent(s) is developed by the promotion of Lewis acid catalysts. In the presence of a catalytic amount of TiCl₂(ClO₄)₂, various carboxylic esters are prepared in high yields through the formation of the corresponding mixed-anhydrides from 3,5-bis(trifluoromethyl)benzoic anhydride and carboxylic acids. The combined catalyst consisting of TiCl₂(ClO₄)₂ together with chlorotrimethylsilane functions as an effective catalyst for the synthesis of carboxylic esters from free carboxylic acids and alcohols with 4-(trifluoromethyl)benzoic anhydride. Various macrolactones are prepared from the free ω-hydroxycarboxylic acids by the combined use of 4-(trifluoromethyl)benzoic anhydride and titanium(IV) catalysts together with chlorotrimethylsilane under mild reaction conditions. The lactonization of trimethylsilyl ω-(trimethylsiloxy)carboxylates using 4-(trifluoromethyl)benzoic anhydride is also promoted at room temperature in the presence of a catalytic amount of TiCl₂(ClO₄)₂. An 8-membered ring lactone, a synthetic intermediate of cephalosporolide D, is successfully synthesized according to this mixed-anhydride method using 4-(trifluoromethyl)benzoic anhydride by the promotion of a catalytic amount of Hf(OTf)₄.     

A study on the synthesis,characterization and properties of polyaniline using acrylic acid as a primary dopant. I: polymerization and polymer

In the presence of acrylic acid (AA) as a primary dopant, polyaniline (PANI) doped with poly(acrylic acid) was successfully synthesized by using ammonium persulfate (APS) as initiator and oxidizing agent. The effect of experimental conditions on the polymer yields was systematically studied. It was found that the polymer yield can be as high as 65%, and this value strongly depends on synthesis conditions, such as the reaction time, the molar ratio of oxidizing agent to aniline monomer, the concentration of reactants and reaction temperature. The molecular weight ( ) of main chains of the de‐doped PANI is estimated to be 32,000–53,000. Based on the data of FT‐IR, UV‐vis, ¹³C‐nuclear magnetic resonance (NMR), elemental analysis and electrical conductivity measurement, the emeraldine salt form of PANI was confirmed and the molecular structure of the resulting PANI‐AA was proposed. Accordingly the reaction mechanism was discussed and it was convinced that the polymerization reaction of AA is initiated by APS. Copyright © 2004 John Wiley & Sons, Ltd.