Synthesis,characterization, and metal ion uptake studies of chelating resins derived from formaldehyde/furfuraldehyde condensed phenolic schiff base of 4,4′‐diaminodiphenylmethane and o‐hydroxyacetophenone

The synthesis, characterization, and metal ion uptake studies of two chelating resins with multiple functional groups are reported. The chelating resins were synthesized by condensing a phenolic Schiff base derived from 4,4′‐diaminodiphenylmethane and o‐hydroxyacetophenone with formaldehyde or furfuraldehyde. The resins readily absorbed transition metal ions, such as Cu²⁺ and Ni²⁺, from dilute aqueous solutions. The Schiff base, resins, and metal polychelates were characterized by various instrumental techniques, such as elemental‐analysis, ultraviolet–visible spectroscopy proton and carbon‐13 nuclear magnetic resonance spectroscopy (¹H‐NMR and ¹³C‐NMR, respectively), X‐ray diffraction (XRD), and thermogravimetric–differential thermogravimetric analyses (TG–DTG). The ¹H‐NMR and ¹³C‐NMR studies were used to determine the sites for aldehyde condensation with the phenolic moiety. Fourier transform infrared data provided evidence for metal–ligand bonding. Thermogravimetric analysis was employed to compare the relative thermal stabilities of the resins and the polychelates. The TG data were fitted into different models and subjected to computational analysis to calculate the kinetic parameters. The XRD data indicate that the incorporation of metal ion into the resin matrix significantly enhanced the degree of crystallinity of the material. The extent of metal‐ion loading into the resins was studied in competitive and noncompetitive conditions, varying the time of contact, metal ion concentrations, and pH of the reaction medium in a suitable buffer medium. The furfuraldehyde‐condensed resin was more effective in removing metal ions than the formaldehyde‐condensed resins. The resins were selective for Cu²⁺, resulting in separation of Cu²⁺ and Ni²⁺ from the mixture at pH 5.89. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 570–581, 2003     

Linear polysulfonates. I. Products of 4,4′-(1-cyclothexylidene) diphenol and 4,4′-(2-norbolidene) diphenol with some aromatic disulfonyl chlorides

Aromatic (poly)cycloaliphatic polysulfonates of high molecular weight can be easily obtained by interfacial polycondensation of aromatic (poly)cycloaliphatic diphenols with aromatic disulfonyl chlorides. The polysulfonates were found to have a low degree of crystallinity, softening ranges in the region 180–310°C and molecular weights in the region: M?_n 3190–4420, and M?_w 19900–83370, thermal stability to above 300°C, and reduced viscosities in the range 0.2–1.00 dL/g.     

Synthesis of 4,4′-aryldihydrazono-3-(3′-pyridyl)-2-pyrazolin-4,5-diones and 1-aryl-3-(3′-pyridyl)-4,4′-arylbisazo-5-aryliminopyrazoles and their application as disazo disperse dyes. Part II

3-(3′-Pyridyl)-2-pyrazoline-4,5-dione 4,4′(4,4′-biphenylenedihydrazone and p-phenylenedihydrazone) and its derivatives ( IIa-e, IIIa-e ) were obtained by the coupling reaction of tetrazotised benzidine and p-diamonobenzene with 3-(3′-pyridyl)-2-pyrazolin-5-ones ( Ia-e ). Similarly, bis-azo compounds containing pyrazole nucleous as, 1-aryl-3-(3′-pyridyl)-4,4′-arylbisazo-5-aryliminopyrazoles ( VIa-i and VIIa-i ) were prepared by the interaction of the corresponding chloro compound ( IV and V ) with aromatic amines. The compounds so obtained ( II, III, VI and VII ) are used as disazo disperse dyes for dyeing polyester fibres fast yellow-orange shades. Their fastness properties towards washing, rubbing, acid-alkaline perspiration and light were investigated.     

An NMR study of the dissociation of N,N′-(2-propyloximino)-4,4′-methylenebis(phenylcarbamate) and its crosslinking of polymers containing labile hydrogens. II

Nuclear magnetic resonance spectroscopy has been used to study the dissociation and reaction of N,N′-(2-propyloximino)-4,4′-methylenebis(phenylcarbamate), as a crosslinking agent for polymers containing labile hydrogens. The crosslinking of poly(acrylic acid), polyacrylamide, and poly(vinyl alcohol) was found to result upon heating each to 150°C for 10 min with this component at 2–10 wt %.     

Effect of monomer composition on properties of copolyimides derived from 3,3′,4,4′‐biphenyltetracarboxylic dianhydride/4,4′‐oxydianiline/1,3‐bis (4‐aminophenoxy)benzene

A series of uncontrolled molecular weight homopolyimides and copolyimides based on 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (s‐BPDA)/4,4′‐oxydianiline (4,4′‐ODA)/1,3‐bis(4‐aminophenoxy)benzene (TPER) were synthesized. All the polyimides displayed excellent thermal stability and mechanical properties, as evidenced by dynamic thermogravimetric analysis and tensile properties testing. A singular glass transition temperature (T_g) was found for each composite from either differential scanning calorimetry (DSC) or dynamic mechanical analysis (DMA), but the values determined from tan δ of DMA were much different from those determined from DSC and storage modulus (E′) of DMA. The Fox equation was used to estimate the random T_g values. Some composites exhibited re‐crystallization after quenching from the melt; upon heating, multi‐melting behavior was observed after isothermal crystallization at different temperatures. The equilibrium melting temperature was estimated using the Hoffman‐Weeks method. Additionally, DMA was conducted to obtain E′ and tan δ. Optical properties were strongly dependent on the monomer composition as evidenced by UV‐visible spectra. X‐ray diffraction was used to interpret the crystal structure. All the results indicated that composites with TPER composition ≥ 70% were dominated by the TPER/s‐BPDA polyimide phase, and ≤40% by the 4,4′‐ODA/s‐BPDA polyimide phase. When the ratio between the two diamines was close to 1:1, the properties of the copolyimides were very irregular, which means a complicated internal structure. Copyright © 2011 Society of Chemical Industry     

Preparation and characterization of novel polyurethanes containing 4,4′‐{oxy‐1,4‐diphenyl bis(nitromethylidine)}diphenol schiff base diol

Four novel segmented polyurethanes (PUs) based on4,4′‐{oxy‐1,4‐diphenyl bis(nitromethylidine)}diphenol (ODBNMD) diol with different diisocyanates such as 4,4′‐diphenylmethane diisocyanate, toluene 2,4‐diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate have been prepared by solution method. The structures of ODBNMD and PUs have been confirmed by Fourier transform infrared (FTIR), nuclear magnetic resonance (¹H‐NMR and ¹³C‐NMR), UV‐visible, and fluorescence spectroscopies. The segmented PUs were further characterized by thermogravimetry (TGA), differential scanning calorimetry (DSC), and wide‐angle X‐ray diffraction. FTIR confirmed hydrogen bonding interactions, whereas TGA and DSC suggested that introduction of aromatic/phenyl ring in the main chain considerably increased the thermal stability. POLYM. ENG. SCI., 54:24–32, 2014. © 2013 Society of Plastics Engineers     

Properties of poly[N,N′-(4,4′-diphenyl ether) 4-amidophthalimide] film

A high molecular weight polyamide–imide polymer derived from the reaction of TMAC–DAPE has been prepared and its film properties have been evaluated. Poly-[N,N′-(4,4′-diphenyl ether) 4-amidophthalimide] film has an excellent combination of mechanical, electrical, and chemical properties at room temperature and at 200°C. A comparison of the film properties of this material with those of a commercial polyimide film, Teflon, FEP, Nomex paper, and Mylar films is also presented.     

Highly fluorinated poly(ether‐imide)s derived from 2,2′‐bis(3,4,5‐trifluorophenyl)‐4,4′‐diaminodiphenyl ether and aromatic dianhydrides

A new diamine, 2,2′‐bis(3,4,5‐trifluorophenyl)‐4,4′‐diaminodiphenyl ether (FPAPE) was synthesized through the Suzuki coupling reaction of 2,2′‐diiodo‐4,4′‐dinitrodiphenyl ether with 3,4,5‐trifluorophenylboronic acid to produce 2,2′‐bis(3,4,5‐trifluorophenyl)‐4,4′‐dinitrodiphenyl ether (FPNPE), followed by palladium‐catalyzed hydrazine reduction of FPNPE. FPAPE was then utilized to prepare a novel class of highly fluorinated all‐aromatic poly(ether‐imide)s. The chemical structure of the resulting polymers is well confirmed by infrared and nuclear magnetic resonance spectroscopic methods. Limiting viscosity numbers of the polymer solutions at 25 °C were measured through the extrapolation of the concentrations used to zero. M_n and M_w of these polymers were about 10 000 and 25 000 g mol^?1, respectively. The polymers showed a good film‐forming ability, and some characteristics of their thin films including color and flexibility were investigated qualitatively. An excellent solubility in polar organic solvents was observed. X‐ray diffraction measurements showed that the fluoro‐containing polymers have a nearly amorphous nature. The resulting polymers had T_g values higher than 340 °C and were thermally stable, with 10% weight loss temperatures being recorded above 550 °C. Based on the results obtained, FPAPE can be considered as a promising design to prepare the related high performance polymeric materials. Copyright © 2011 Society of Chemical Industry     

Preparation of poly(amic acid) and polyimide derived from 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride with different diamines by microwave irradiation

Polycondensation‐type poly(amic acid) (PAA) was synthesized with 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride as a dianhydride monomer and 4,4′‐diaminodiphenylmethane and 4,4′‐oxydianiline as diamine monomers under microwave irradiation in dimethylformamide. Then, PAA was used to make polyimide (PI) by imidization at a low temperature. The structure and performance of the polymers were characterized with Fourier transform infrared (FTIR), proton nuclear magnetic resonance (¹H‐NMR), viscosity, X‐ray diffraction (XRD), and thermogravimetry (TG) curve analyses. The FTIR spectra of the polymers showed characteristic peaks of PI around 1779 and 1717 cm^?1. The ¹H‐NMR spectrum of PAA indicated a singlet at 6.55 ppm assigned to ? NHCO? and a singlet at 10.27 ppm assigned to carboxylic acid protons. The XRD spectrum demonstrated that the obtained PI had a low‐order aggregation structure with a d‐spacing of 0.5453 nm. The TG results revealed that the PI was thermally stable with 10% weight loss at 565°C in an N₂ atmosphere. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Chemical modification of 3,3′,4,4′‐biphenyltetracarboxylic dianhydride polyimides by a catechol‐derived bis(ether amine)

Having previously demonstrated that the polyimide derived from 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA) and 1,2‐bis(4‐aminophenoxy)benzene [termed triphenyl ether catechol diamine (TPEC)] exhibited superior tensile properties in addition to good thermal properties, we now provide a preliminary assessment of the properties of the copolyimides prepared from BPDA, TPEC, and another aromatic diamine. The homopolyimides derived from BPDA and many aromatic diamines generally possessed good mechanical properties and thermal properties; however, they were insoluble in available organic solvents. In several cases, organosoluble BPDA copolyimides could be prepared from BPDA and equimolar mixtures of TPEC and another aromatic diamine. All the copolyimides could be formed into tough films with high moduli and strengths and, in most cases, high extensions to break. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 351–358, 2002; DOI 10.1002/app.10342     

Ambipolar and multi‐electrochromic polyimides based on N,N‐di(4‐aminophenyl)‐N′,N′‐diphenyl‐4,4′‐oxydianiline

A series of novel aromatic polyimides were synthesized from N,N‐di(4‐aminophenyl)‐N′,N′‐diphenyl‐4,4′‐oxydianiline and aromatic tetracarboxylic dianhydrides through a conventional two‐step procedure. Most of the polyimides exhibited reasonable solubility in organic solvents and could afford robust films via solution casting. The polyimides exhibited high thermal stability, with glass transition temperatures in the range 227–273 °C and 10% weight‐loss temperatures in excess of 550 °C. All the polyimide films showed ambipolar redox and multi‐electrochromic behaviors. They exhibited two reversible oxidation redox couples at 0.94–0.98 and 1.09–1.12 V versus Ag/AgCl in acetonitrile solution. A coupling reaction between the radical cations of the pendent triphenylamine units occurred during the oxidative process forming a tetraphenylbenzidine structure which resulted in an additional redox state and color change. © 2014 Society of Chemical Industry     

New organic polymers,II. Synthesis and characterization of poly[3,3′-(6,6′-bis-(2-substituted-4-quinazolonediyl)) alkylene]s

Poly[3,3′-(6,6′-bis-(2-substituted-4-quinazolonediyl))alkylene]s have been synthesized by reacting 6,6′-bis-(2-R-3,1,4-benzoxazinone) (R = Me, Ph, and ? CH₂Ph) with aliphatic diamines H₂N(CH₂)_nNH₂ with n = 0, 2, 3, 4, 6 and 8 in m-cresol. These polymers are insoluble in all common organic solvents but are fairly soluble in concentrated sulfuric acid. The polymers were characterized by IR spectral study, viscometric measurements and thermal analysis. IR spectra of the polymer samples have been compared with those of their model compounds.     

Thermal properties of poly[N,N′-(4,4′-diphenyl ether) 4-amidophthalimide] film

The aging behavior of a polyamide–imide film was investigated. Film samples have been exposed to temperatures from 225° to 350°C for various times and the mechanical and electrical properties measured. This information was used to construct log life plots to gain an insight into the service life of this material. TGA and DTA results coupled with the information from the aging tests indicate that this film can be used at temperatures of 180° to 200°C for extended periods of time. Mechanical properties, especially elongation, of the film deteriorate faster than the electrical properties.     

Synthesis and characterization of novel polyaspartimides derived from 2,2′‐dimethyl‐4,4′‐bis(4‐maleimidophenoxy)biphenyl and various diamines

A novel bismaleimide, 2,2′‐dimethyl‐4,4′‐bis(4‐maleimidophenoxy)biphenyl, containing noncoplanar 2,2′‐dimethylbiphenylene and flexible ether units in the polymer backbone was synthesized from 2,2′‐dimethyl‐4,4′‐bis(4‐aminophenoxy)biphenyl with maleic anhydride. The bismaleimide was reacted with 11 diamines using m‐cresol as a solvent and glacial acetic acid as a catalyst to produce novel polyaspartimides. Polymers were identified by elemental analysis and infrared spectroscopy, and characterized by solubility test, X‐ray diffraction, and thermal analysis (differential scanning calorimetry and thermogravimetric analysis). The inherent viscosities of the polymers varied from 0.22 to 0.48 dL g⁻¹ in concentration of 1.0 g dL⁻¹ of N,N‐dimethylformamide. All polymers are soluble in N‐methyl‐2‐pyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide, dimethylsulfoxide, pyridine, m‐cresol, and tetrahydrofuran. The polymers, except PASI‐4, had moderate glass transition temperature in the range of 188°–226°C and good thermo‐oxidative stability, losing 10% mass in the range of 375°–426°C in air and 357°–415°C in nitrogen. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 279–286, 1999     

Two novel Zn(II) coordination polymers based on trigonal ligand: 4′-(4-pyridyl)-3,2′:6′,3″-terpyridine

Two novel Zn(II) coordination polymers, [Zn₅(pytpy)₈(fum)₄(H₂O)₄(OH)₂]_n · n(CH₃OH) · 2n(H₂O) (1) and [Zn₃(pytpy)₄ (btc)₂]_n · 2n(H₂O) (2) (pytpy = 4′-(4-pyridyl)-3,2′:6′,3″-terpyridine, H₂fum = fumaric acid, H₃btc = 1,3,5-benzenetricarboxylic acid) have been hydrothermally synthesized and structurally characterized. Complex 1 is a 2D layer structure, which is constructed from linear pentanuclear Zn(II) subunits interconnected via bidentate-bridging pytpy ligands and tridentate-bridging fum²⁻ anions. Complex 2 is a 3D network structure, μ₂-pytpy ligands link the layers based on the heart-like hexanuclear subunits to form the 3D network. Both complexes show strong fluorescence emission upon excitation at 310 nm in solid state. Additionally, these two complexes possess great thermal stabilities, especially for 2, the framework is stable up to 350 °C.     

Solution NMR study of the post-polymerization crosslinking agent N,N′-(2-propyloximino)-4,4′-methylenebis(phenylcarbamate). I

Because of its possible use as a blocked “post-polymerization crosslinking agent” for polymers containing labile hydrogen, the structure of the acetone oxime adduct of 4,4′-methylenebis-(phenylisocyanate) has been determined. ¹³C and ¹H nuclear magnetic resonance (NMR) spectroscopy has identified this product to be N,N′-(2-propyloximino)-4,4′-methylenebis(phenylcarbamate). Chemical shift assignments were based on information obtained by proton decoupled, off-resonance decoupled, and gated decoupled ¹³C-NMR, proton-NMR, and semiemperical substituent chemical shift (SCS) parameters.     

New thermoplastic segmented polyurethanes with hard segments derived from 4,4′‐diphenylmethane diisocyanate and methylenebis(1,4‐phenylenemethylenethio)dialcanols

New thermoplastic poly(ether–urethane)s and poly(carbonate–urethane)s were synthesized by a one‐step melt polymerization from poly(oxytetramethylene) diol (PTMO) and poly(hexane‐1,6‐diyl carbonate) diol (PHCD) as soft segments, 4,4′‐diphenylmethane diisocyanate, and 2,2′‐[methylenebis(1,4‐phenylenemethylenethio)]diethanol, 3,3′‐[methylenebis(1,4‐phenylenemethylenethio)]dipropan‐1‐ol or 6,6′‐[methylenebis(1,4‐phenylenemethylenethio)]dihexan‐1‐ol as unconventional chain extenders. The effects of the kind and amount of the polymer diol and chain extender used on the structure and properties of the polymers were studied. The polymers were examined by Fourier transform infrared (FTIR) spectroscopy, X‐ray diffraction analysis, atomic force microscopy, differential scanning calorimetry, thermogravimetric analysis (TGA), TGA coupled with FTIR spectroscopy, and Shore hardness and tensile testing. The obtained high‐molecular‐weight polymers showed elastomeric or plastic properties. Generally, the PTMO‐based polymers exhibited significantly lower glass‐transition temperatures (up to ?48.1 vs ?1.4°C), a higher degree of microphase separation, and ordering in hard‐segment domains in comparison with the corresponding PHCD‐based ones. Moreover, it was observed that the polymers with the PTMO soft segments showed poorer tensile strengths (up to 36.5 vs 59.6 MPa) but higher elongations at break. All of the polymers exhibited a relatively good thermal stability. Their temperatures of 1% mass loss were in the range 270–320°C. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Coordination polymers, 1. Magnetic,spectral, and thermal properties of coordination polymers derived from terephthalaldehyde bis(S-benzyldithiocarbazate)

New Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) coordination polymers of Schiff base ligand derived from terephthalaldehyde and S-benzyldithiocarbazate have been synthesized in DMF media. The coordination polymers have been characterized by their elemental analysis, magnetic susceptibility, and by electronic and infrared spectral measurements. The thermal stability of each polymer was found out by thermogravimetric analysis. The thermal stability of coordination polymers obtained from thermograms has the following order: $ {\rm Zn} \simeq {\rm Fe} > {\rm Co} > {\rm Ni} > {\rm Min} \simeq {\rm Cu}$ Mn(II), Fe(II), Co(II), and Ni(II) coordination polymers are of a six-coordinated octahedral structure while Cu(II) and Zn(II) coordination polymers are found to be four-coordinated square planar and tetrahedral structure, respectively. The ligand-field and nephelauxetic parameters have been determined from the spectra, using ligand-field theory of spin-allowed transitions which are found consistent with six-coordinate structure for Mn(II), Fe(II), Co(II), and Ni(II) coordination polymers. Elemental analyses indicates a ligand: metal ratio of 1 : 1 in all the coordination polymers and the association of water molecules with central metal atom in case of Mn(II), Fe(II), Co(II), and Ni(II) coordination polymers.     

Linear polymers with sulfur in the main chain,I . Polyesters derived from interfacial polycondensation of 4,4′-thiodiphenol and/or bisphenol-A with adipoyl dichloride

Polyesters having sulfur atoms in the main chain were synthesized from 4,4′-thiodiphenol (TDP) and adipoyl dichloride (APC) by both solution polycondensation and interfacial polycondensation. The specific viscosity of the product from interfacial polycondensation was higher than that of the product obtained by the solution method. Influences of solvent and phase transfer catalyst on the specific viscosity were investigated in the interfacial polycondensation. As for viscosity, the polyester synthesized with 1,1,2,2-tetrachloroethane (TCE) as the organic phase and tetra-n-butylammonium bromide (Bu₄NBr) as the catalyst indicates the highest value. Bisphenol-A was co-polycondensated with TDP and APC to improve the toughness of the polyester from TDP. Properties of the polymers were evaluated with thermogravimetric analysis, differential scanning calorimetry, FTIR and ¹H NMR spectroscopic analysis, viscoelastic spectrometer (DMA), oxygen gas permeability (GTR), and gel permeation chromatography. The polyesters have a very low value of oxygen gas permeability; especially the value of the polyester from TDP and APC was lower than that of PET.     

The behaviour of commercially important diisocyanates in fire conditions. Part 2: Polymeric diphenyl methane-4,4′-diisocyanate (pmdi)

The behaviour of polymeric diphenyl methane-4,4′-diisocyanate (PMDI) is described when examined in a laboratory small-scale test for its reaction to fire (ease of ignition; heat release and toxic gas production). Full-scale real fire scenarios have also been staged to predict events if (1) drumstock PMDI and (2) sizeable pools of liquid PMDI become enveloped in a fire. PMDI requires a stimulus (e.g. heat) before it will ignite from an applied flame. It then burns in a self-sustaining manner for a few minutes, during which main emissions take place. Then a polymerization reaction begins, producing a low density non-burning residue, which progressively dampens down the burning events by blanket action. Residues of 30–80% sample weight were recorded. The major toxic gas produced is carbon monoxide, though free isocyanate is to be expected in the early stages of the fire, and hydrogen cyanide could be important, especially in well-developed fire conditions. Firefighters should therefore wear full protective clothing and fresh-air breathing equipment. Events when drums of PMDI are exposed to fire depend heavily on the characteristics of the containers, with some rupture steps proceeding with considerable violence. Drumstock PMDI should be stored separately from easily ignitable materials.