Addition polyimides. II. Synthesis and characterization of bisitaconimide prepolymers

N,N′-bis(3,3′-itaconimidophenyl) sulfone has been synthesized by reacting itaconic anhydride with 3,3′-diamino diphenyl sulfone. The bisitaconimides and the intermediates were characterized by chemical analysis, IR, NMR, TG, and GPC. The degree of polymerization (DP) of the prepolymers of the bisitaconimide was followed by GPC and from the NMR data on vinylidene and aromatic proton ratios. The correlation between DP and intrinsic viscosity of the prepolymers was made use of to determine the Mark–Houwink constants (K and α). The thermal stability and the decomposition kinetics of the prepolymers were evaluated from TG data. The kinetic parameters, viz. energy of activation, E, and preexponential factor A, were computed using four nonisothermal integral equations, and their values are not appreciably affected by the degree of polymerization, within the range studied.     

4,4′-carbo(4,4′-bismaleimido phenoxy)diphenyl silane: Synthesis and characterization

The paper describes the successful synthesis of silicon containing bismaleimide resin 4,4′-carbo(4,4′-bismaleimido phenoxy)diphenyl silane. The char yield of the bismaleimide resin in N₂ atmosphere was found to be 55% at 800°C. Chain extension of bismaleimide with 4,4′-diamino diphenyl sulfone reduced the char yield and thermal stability.     

Effects of water sorption at different temperatures on permanent changes in an epoxy

Crosslinked epoxy resins, tetraglycidyl 4,4′-diamino diphenyl methane cured with 4,4′-diamino diphenyl sulfone, were soaked in water at either 25°C or 70°C for varying lengths of time. The infrared spectra and DSC thermograms were obtained for samples that were soaked, or soaked and dried. There was a monotonic decrease in exothermic reaction energy with water content. The glass transition was also lowered, although samples soaked at 70°C showed a leveling in the T_g around 115°C. When the soaked samples were dried, the exothermic reaction energy showed near reversibility for samples soaked at 25°C while the 70°C samples were highly irreversible. IR of the latter samples showed that the 70°C water soaking resulted in reaction of some of the unreacted epoxide groups that remained after the initial cure.     

Synthesis and characterization of poly(ether sulfone) and poly(ether sulfone ketone) copolymers

Poly(ether sulfone) and poly(ether sulfone ketone) copolymers (I–V) were synthesized by the nucleophilic substitution reaction of 4,4′-dihydroxy diphenyl sulfone (DHDPS, A) with various mole proportions 4,4′-difluoro benzophenone (DFBP, B) and 4,4′-difluoro diphenyl sulfone (DFDPS, C) using sulfolane as solvent in the presence of anhydrous K₂CO₃. The polymers were characterized by physicochemical and spectroscopic techniques. All polymers were found to be amorphous, and the glass transition temperature (T_g) was found to increase with the sulfonyl content of the polymers. ¹³C-nuclear magnetic resonance (NMR) spectral data was interpreted in terms of the compositional triads, BAB, BAC, CAC, ABA, and ABB, and indicate that transetherification occurs at high concentration of DFBP units in the polymer (IV). The good agreement between the observed and calculated feed ratios validates the triad analysis. Thermal decomposition studies reveal that the thermal stability of the polymers increases with increase in the carbonyl content in the polymer. Activation energies for thermal decomposition were found to be in the range of 160–203 kJ mol⁻¹ with the cleavage of ϕ SO₂ bond being the preponderant mode of decomposition and depended on the block length of the sulfonyl unit. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2113–2121, 1999     

A simple imide compound as a curing agent for epoxy resin. I. Synthesis and properties

A simple imide compound, 4‐amino‐phthalimide (APH), was synthesized as a curing agent for epoxy resin. APH was prepared from the hydration of 4‐nitro‐phthalimide, which was prepared from the nitration of phthalimide. The chemical structure of APH was verified by IR and ¹H‐NMR spectra. The thermal properties and dielectric constant (ε) of a phosphorus‐containing novolac epoxy resin cured by APH were determined and compared with those of epoxy resins cured by either 4,4′‐diamino diphenyl methane (DDM) or 4,4′‐diamino diphenyl sulfone (DDS). The results indicate that the epoxy resin cured by APH showed better thermal stability and a lower ε than the polymer cured by either DDM or DDS. This was due to the introduction of the imide group of APH into the polymer structure. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Cure kinetics of ternary blends of epoxy resins studied by nonisothermal DSC data

The curing kinetics of blends of diglycidyl ether of bisphenol A (DGEBA), cycloaliphatic epoxy resins, and carboxyl‐terminated butadiene‐acrylonitrile random copolymer (CTBN) in presence of 4,4′‐diamino diphenyl sulfone (DDS) as the curing agent was studied by nonisothermal differential scanning calorimetry (DSC) technique at different heating rates. The kinetic parameters of the curing process were determined by isoconversional method given by Malek for the kinetic analysis of the data obtained by the thermal treatment. A two‐parameter (m, n) autocatalytic model (Sestak‐Berggren equation) was found to be the most adequate selected to describe the cure kinetics of the studied epoxy resins. The values of E_a were found to be 88.6 kJ mol^?1 and 61.6 kJ mol^?1, respectively, for the studied two sample series. Nonisothermal DSC curves obtained using the experimental data show a good agreement with that theoretically calculated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Molecularly imprinted polymer for solid phase extraction of nicotinamide in pork liver samples

Aromatic polyamides and polythioamides with pendent chlorobenzylidine rings were synthesized through direct polycondenzation of 2‐(p‐chlorobenzalimino) terephthalic acid with the diamines 4,4′‐oxidianiline (1a), 4,4′‐methylenediamide (1b), 4,4′‐diaminodiphenyl sulfone (1c), and thioamines 4,4′‐(bisthiourea) diphenyl ether (3a), 4,4′‐(bisthiourea) diphenyl methane (3b), 4,4′‐(bisthiourea) diphenyl sulfone (3c), respectively, in DMF using P(OPh)₃/pyridine. The polymers were precipitated using water as nonsolvent. FTIR and ¹H‐NMR spectroscopic analysis was used to characterize the monomers and polymers. Representative polyamides and polythioamides were used for the removal of heavy metal ions such as Pb(II), Cd(II), Cu(II), and Cr(III) from aqueous solutions. The effects of pH, contact time, and initial concentration on the uptake of metal ions have been investigated. The adsorption capacities under competitive conditions were in the order Pb (II) > Cu (II) > Cr (III) > Cd (II). The adsorbed ions were eluted by treatment with 2N HCl, and the activities of the polymers are retained after fourth regeneration. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Improvement of Elastic Modulus and Thermal Stability of Epoxy Resin Using New Curing Agents

New curing agents 2,5-diamino-1,3,4-thiadiazole (DATD) and N-(4-hydroxybenzal) N'(4′-hydroxyphenyl) thiourea (HHPT) were synthesised and characterized using FT-IR, 1H-NMR and 13C-NMR analysis. The curing reactions were studied for the epoxy resin diglycidyl ether of bisphenol-A (DGEBA) using new curing agents along with the conventional aromatic diamine 4,4′-diamino diphenyl methane (DDM) for comparison purpose. The curing profiles of DDM, DATD and DATD/HHPT towards DGEBA were examined by Differential Scanning Calorimetry (DSC). Elastic modulus and thermal stability of the cured resins were evaluated using DMA and TGA analysis. When compared with DDM and DATD, the DATD/HHPT curing system accelerated the curing rate due to the presence of phenol molecules in the HHPT. Furthermore, the DATD/HHPT-cured epoxy resin demonstrated higher elastic modulus along with better thermal stability.     

Studies on the curing kinetics and thermal stability of the novel tetrafunctional epoxy resin N,N,N′N′-tetrakis(2,3-epoxypropyl)-4,4′-(1,4-phenylenedioxy)dianiline

A novel tetrafunctional epoxy resin, namely N,N,N′N′-tetrakis(2,3-epoxypropyl)-4,4′-(1,4-phenylenedioxy)dianiline, has been synthesized. The curing kinetics has been studied by differential scanning calorimetry (DSC) using various amine curing agents. Thermal stabilities of the cured products have been investigated by thermogravimetric (TG) analyses. The overall activation energies for the curing reactions are observed to be in the range 63.6–196.7 kJ·mol^–1. The cured products have good thermal stability.     

Crystal structure,curing kinetics,and thermal properties of bisphenol fluorene epoxy resin

Diglycidyl ether of 9,9‐bis(4‐hydroxyphenyl) fluorene (DGEBF) monomer was successfully synthesized and characterized in detail. The crystal structure of DGEBF was measured by single‐crystal X‐ray diffraction analysis. Curing kinetics of DGEBF with 4,4‐diaminodiphenyl sulfone (DDS), thermal properties, and decomposition kinetics were investigated using nonisothermal differential scanning calorimetry (DSC) according to Kissinger, Ozawa and Crane methods. The glass transition temperature (T_g), thermal properties of cured polymer were estimated by DSC, dynamic mechanical analysis, and thermogravimetric analyses. Epoxy value of DGEBF monomer up to theoretical value leads to higher crosslink density of cured polymers. The cured DGEBF/DDS system exhibited obvious higher T_g and better thermal stability compared to those of DGEBF/diamine systems reported previously. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

New polymer syntheses: XV. Synthesis and characterization of new polyketoamine polymers containing ether or thioether linkages in the main chain

An interesting new class of linear polyketoamine polymers containing ether or thioether linkages in the main chain has been synthesized by solution polycondensation of 4,4′‐bis(chloroacetyl)diphenyl ether ( I ), 4,4′‐bis(chloroacetyl)diphenyl sulfide ( II ) and 4,4′‐bis(chloroacetyl)diphenyl sulfone ( III ) with various aliphatic and aromatic diamines. The model compounds IV, V and VI were synthesized from the monomers I, II and III with aniline in dry benzene and their structures were confirmed by elemental and spectral analyses. The resulting polymers were characterized by elemental and spectral analyses, as well as by solubility and viscometry measurements. The thermal properties were evaluated by TGA and DSC and correlated to their structural units. X‐ray analysis showed that the polymers had some degree of crystallinity in the region 2θ = 5° to 60°. The UV‐visible spectra of some selected polymers were measured in dimethylsulfoxide (DMSO) solution and showed absorption bands in the range 260–475 nm, due to n–π* and π–π* transition. In addition, the morphological properties of selected examples were tested by SEM, and the electrical properties of these polymers were measured. Copyright © 2005 Society of Chemical Industry     

Synthesis and properties of poly(aryl ether sulfone ether ketone ketone) (PESEKK)

4,4′‐bis(Phenoxy)diphenyl sulfone (DPODPS) was synthesized by reaction of phenol with bis(4‐chlorophenyl) sulfone in tetramethylene sulfone in the presence of NaOH. Two poly(aryl ether sulfone ether ketone ketone)s (PESKKs) with high molecular weight were prepared by low temperature solution polycondensation of DPODPS and terephthaloyl chloride (TPC) or isophthaloyl chloride (IPC), respectively, in 1,2‐dichloroethane and in the presence of aluminum chloride (AlCl₃) and N‐methylpyrrolidone (NMP). The resulting polymers were characterized by various analytical techniques, such as FT‐IR, ¹H‐NMR, DSC, TG, and WAXD. The results show that the T_g and T_d of PESEKKs are much higher, but its T_m is lower than those of PEKK. The other results indicate that PESEKKs exhibit excellent thermostabilities at 300 ± 10°C. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 489–493, 2005     

Dynamics and thermal properties of epoxy resin cured by new diamino disiloxanes

Two disiloxane compounds, 3,3′‐(1,3‐dimethyl‐1,3‐diphenyl‐1,3‐disiloxanediyl)bis(benzenamine) ( C1 ) and 4,4′‐(1,3‐dimethyl‐1,3‐diphenyl‐1,3‐disiloxanediyl)bis(benzenamine) ( C2 ) were synthesized and used as new curing agents of DGEBA epoxy resin with an epoxy value of 0.51 ( E‐51 ). The curing kinetics of E‐51/C1 and E‐51/C2 systems was investigated by non‐isothermal differential scanning calorimetry (DSC) analyses. The activation energy (ΔE) and the characteristic cure temperatures of the two systems were determined. The two systems have the similar activation energy. The reactivity of E‐51/C1 is higher than that of E‐51/C2 . The reaction orders of E‐51/C1 and E‐51/C2 are 0.88 and 0.87, respectively, illustrating that curing reaction between the epoxy resin and curing agent ( C1 or C2 ) is complicated. The DSC result shows that E51 cured by C2 has higher Tg; whereas thermogravimetric analysis results indicate that E51 cured by C1 has higher thermal stability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42385.     

Synthesis and characterization of a novel phthalazinone poly(aryl ether sulfone ketone) with carboxyl group

Soluble, thermally stable phthalazinone poly(aryl ether sulfone ketone)s (PPESKs) containing a carboxyl group in its side chain have been synthesized by the nucleophilic displacement reaction of 4‐(4‐hydroxylphenyl)‐1(2H)‐phthalazinone with bis(4‐chlorophenyl) sulfone, 4,4′‐difluoro‐benzophenone, and phenolphthalin. The polymerization reactions were conducted in sulfolane in the presence of K₂CO₃ to give high molecular weight polymers, which are soluble in solvent such as nitrobenzene and pyridine at room temperature and easily cast into flexible, yellow, and transparent film. The polymers are amorphous with high glass transition temperature. The decomposition temperature of the polymers are >400°C, which indicates high thermal stability. The crosslinking reaction of PPESK can occur by using dicyandiamide (Dicy) as curing agent. The apparent energy (ΔE) is 52.2 kJ/mol and reaction order (n) is close to 1.0. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1111–1114, 2003     

Photodegradable polymers: Poly(arylene keto amine)s

Low-molecular-weight poly(arylene keto amines) were prepared from the polymerization of 4,4-bis(chloroacetyl)diphenyl ether, 4, 4′-bis(bromoacetyl) diphenyl ether, and 4,4′-bis(2-bromopropionyl) diphenyl ether with piperazine, 4, 4′-trimethylenedipiperidine, and N, N′-dimethyl-1,3-propanediamine. These film-forming polymers and suitable monomeric model compounds were found to be degraded by photolysis. The poly(keto amines) resisted degradation by the fungi As-pergillus niger and Aspergillus flavus.     

Novel Copolyamides Based on s-Triazine Derivatives

Ten copolyamides have been synthesized by polycondensation of 2-(N-methylpiperazine)-4,6-bis(2-naphthoxy-6-carbonyl chloride)-s-triazine [MPNCCT] and different mixtures of diamines such as; 4,4′-diamino diphenylamide [DADPA] + 4,4′-diamino diphenyl sulphone [DADPS]; 4,4′-diamino diphenylamide [DADPA] + 4,4′-diamino diphenylmethane [DADPM]; 4,4′-diaminodiphenylamide [DADPA] + p-phenylene diamine [PPDA]; 4,4′-diaminodiphenylamide [DADPA] + ethylene diamine [EDA]; 4,4′-diaminodiphenylamide [DADPA] + 2,4-diamino toluene [DAT]; 2,4-diamino toluene [DAT] + 4,4′-diaminodiphenyl sulphone [DADPS]; 2,4-diamino toluene [DAT] + 4,4′-diaminodiphenyl sulphonamide [DADPSA]; 2,4-diamino toluene [DAT] + 4,4′-diaminodiphenyl methane [DADPM]; 2,4-diamino toluene [DAT] + o-phenylene diamine [OPDA] and p-phenylene diamine [PPDA] + 4,4′-diaminodiphenyl sulphonamide [DADPSA]. All the copolyamides have been characterized by IR spectra, NMR spectra, solubility, density, viscosity measurements and thermogravimetric analysis [TGA]. The obtained products, have high thermal stability along with good solubility in organic solvents.     

Epoxy thermosetting systems: Dynamic mechanical analysis of the reactions of aromatic diamines with the diglycidyl ether of bisphenol A

Dynamic mechanical behavior during the reactions of four aromatic diamines (m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone, and benzidine) with the diglycidyl ether of bisphenol A was studied by torsional braid analysis under isothermal conditions. Depending on the cure temperature, three types of behavior were observed: (I) below T_gg (the glass transition temperature of the reactive systems at the gel point); (II) between T_gg and T_g∞ (the glass transition temperature of the ultimately cured polymers); (III) above T_g∞. Overall activation energies and apparent overall rate constants of the cure reactions based on third-order overall kinetics were determined before gelation, after gelation but before vitrification, and after vitrification, using gelation time, relative rigidity, and glass transition temperature T_g(t) of the polymers as kinetic terms. The influence of cure temperature and structure of the diamines on the kinetic parameters is discussed.     

Thermal degradation of polymers. XIV. Thermal analysis studies in air on homopolymers of m-N,N-dimethylaminostyrene and p-N,N-diethylaminostyrene and their copolymers with styrene

Homopolymers of m-N,N-diethylaminostyrene and p-N,N-diethylaminostyrene and their copolymers with styrene have been subjected to thermal analysis studies in air. Molecular weight and copolymer composition have been shown to influence the stability of the polymers and the shape of the TG and DSC curves in the case of polymers containing m-N,N-dimethylaminostyrene. Polymers containing p-N,N-diethylaminostyrene show TG and DSC curves essentially independent of molecular weight and copolymer composition. The behavior of the two systems is discussed in terms of the antioxidant effect of the chain-bound N,N-dialkylamino substituents and their secondary reactions.     

Synthesis and properties of fluoro‐polyetherimides

A series of amorphous fluoro‐polyetherimides based on 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluropropane dianhydride (6FDA) and di‐ether‐containing diamines 4,4′‐bis(3‐aminophenoxy)diphenyl sulfone (m‐SED), 4,4′‐bis(4‐aminophenoxy)diphenyl sulfone (p‐SED), 4,4′‐bis(4‐aminophenoxy)diphenyl propane (BPADE) were synthesized. These melt processable polyetherimide polymers from p‐SED and BPADE showed excellent electrical properties. The dielectric constants, 2.74 and 2.65 at 10 MHz respectively, are lower than commercially available polyetherimide ULTEM® 1000, and polyimide Kapton® H films. In addition, we found that trifluoromethyl groups‐containing polyimides not only show extraordinary electrical properties, but they also exhibit excellent long‐term thermo‐oxidative stability and reduced water absorption relative to non‐fluorinated polyimides. The weight retention of these fluoro‐polyetherimides at 315°C for 300 h in air varies from 93% to 98%. Whereas, their moisture absorption at 100 RH at 50°C was in the range of 0.3% to 1.05%, which is much lower than those of Ultem 1000 and Kapton H. In the case of fluoro‐polyetherimides from p‐SED and m‐SED (para and meta isomers) diamines with ‘ether’ and sulfonyl (‐SO₂‐) spacer groups, the d‐spacing and T_g values decreased from 4.72Å to 4.56Å and 293°C to 244°C respectively. Similarly, the transparency of these polymer films (in the range of 80% to 90%) at 500 nm solar wavelength was higher than Ultem 1000 and Kapton H.     

Synthesis and thermal cure of diphenyl ethers terminated with acetylene and phenylacetylene

Two kinds of novel compounds, diphenylacetylene diphenyl ether (DPADPE) and diacetylene diphenyl ether (DADPE), were prepared and polymerized under heating. Raman, DSC and ¹³C CP/MAS NMR analyses were used for studying the polymerization reaction. DPADPE and DADPE have melting points at 190 and 79 °C, with exothermic peaks of the DSC curves at 375 and 215 °C for curing, respectively. Raman and ¹³C CP/MAS NMR spectra show that DPADPE could be cured at a temperature higher than 300 °C and DADPE at a lower temperature of higher than 150 °C. The kinetic parameters for the thermal crosslinking reactions were obtained by the Ozawa method and the results show that the apparent activation energy is 152 kJ mol^?1 for DPADPE and 109 kJ mol^?1 for DADPE. An ene–yne Straus product appears in the cured DADPE, whereas this product has not been identified in the cured DPADPE. The cured DPADPE and DADPE demonstrate good thermal and thermo‐oxidative stability. Copyright © 2006 Society of Chemical Industry