3,5-二氧基苯甲酰哌嗪和均苯三甲酰氯界面聚合法制备复合纳滤膜

A new aromatic diamine,3,5-diaminobenzoylpiperazine (3,5-DABP),was synthesized from 3,5-diaminobenzoic acid and 1-formyl piperazine.The structure of 3,5-DABP was identified by FT-IR spectra and 1H NMR spectra.With 3,5-DABP as aqueous monomer and trimesoyl chloride (TMC) as organic monomer,thin film composite (TFC) nanofiltration membranes were prepared by interfacial polymerization technology.The salt rejection order of these TFC membranes is Na2SO4>MgSO4>MgCl2>NaCl.This sequence indicates that the membranes are negatively charged.     

Permselectivities of 2,2′‐dimethyl‐4,4′‐bis(aminophenoxyl)biphenyl diphenyl methane–based aromatic polyamide membranes for aqueous alcohol mixtures in pervaporation and evapomeation

The separation of aqueous alcohol mixtures was carried out by use of a series of novel aromatic polyamide membranes. The aromatic polyamides were prepared by the direct polycondensation of 2,2′‐dimethyl‐4,4′‐bis(aminophenoxyl)biphenyl (DBAPB) with various aromatic diacids, such as terephthalic acid (TPAc), 5‐tert‐butylisophthalic acid (TBPAc), and 4,4′‐hexafluoroisopropylidenedibenzoic acid (FDAc). The pervaporation and evapomeation performance of these novel aromatic polyamide membranes for dehydrating aqueous alcohol solution were investigated. The solubility of ethanol in the aromatic polyamide membranes is higher than that of water, but the diffusivity of water through the membrane is higher than that of ethanol. The effect of diffusion selectivity on the membrane separation performances plays an important role in the evapomeation process. Compared with pervaporation, evapomeation effectively increases the permselectivity of water. Moreover, the effect of aromatic diacids on the polymer chain packing density, pervaporation, and evapomeation performance were investigated. It was found that the permeation rate could be increased by introduction of a bulky group into the polymer backbone. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2688–2697, 2003     

The solid-phase synthesis of dendritic polyamides

Summary The solid-phase synthesis of hyperbranched dendritic polyamides was attempted using two different monomers based on 3,5-diaminobenzoic acid. Growth of the dendritic molecules past the fourth generation was extremely sluggish. The hyperbranched molecules were cleaved from the solid support and examined by gel permeation chromatography, and other spectroscopic methods.     

Synthesis and characterization of polyamides containing arylene sulfide-sulfone groups

Polyamides containing arylene sulfide as well as arylene sulfide-sulfone linkages were prepared from bis(4-phenylthio)dibenzoyl chloride (BPCl), 4,4′-[sulfonylbis(4-phenylthio)]dibenzoyl chloride (SPCl) and aromatic diamines both by solution and interfacial polymerization techniques. In the solution polymerization the effect of two different acid acceptors, lithium chloride and triethylamine, on inherent viscosity of the polyamides was studied. The effect of aromatic sulfone ether diamines and conventional aromatic diamines on viscosity and thermal properties of polyamides was also investigated. The polyamides prepared were characterized by IR, ¹H NMR, elemental analysis, solution viscosity, thermogravi-metry, differential scanning calorimetry and X-ray diffraction. Thermal and physical properties of polyamides prepared from BPCl and SPCl were compared.     

Synthesis and Properties of Novel Polycyanurates Derived from 2-(N-piperidino)-4,6-bis (naphthoxy-2-carbonyl chloride)-s-triazine

Various polyamides containing s-triazine rings in the main chain were synthesized by high temperature polycondensation of 2-(N-piperidino)-4,6-bis(naphthoxy-2-carbonyl chloride)-s-triazine [PNCCT] with various aromatic diamines such as 4,4′-diaminodiphenyl [DADP], 4,4′-diaminodiphenylamide [DADPA], 4,4′-diaminodiphenylsulphone [DADPS], 4,4′-diaminodiphenylsulphonamide [DADPSA], 4,4′-diaminodiphenyl methane [DADPM], 2,4-diamino toluene [DAT] and p-phenylene diamine [PPDA]. All the polyamides were characterized by viscosity measurements, IR spectra, NMR spectra, and thermogravimetric analysis.     

三芳胺类空穴传输材料的合成及光电性能

以3,5-二甲基苯胺为原料与苯磺酸钠反应合成了3,5-二甲基二苯胺,研究了反应温度、时间以及反应物配比对收率的影响,确定了最佳工艺条件。再以3,5-二甲基二苯胺与4,4'-二碘联苯通过Ullmann缩合反应合成了空穴传输材料N,N′-双(3,5-二甲基苯基)-N,N′-二苯基-1,1′-联苯-4,4′-二胺,产品收率为82.24%,经提纯,产品纯度可达99.31%。对该化合物进行的光电测试结果表明,其具有优异的空穴传输性能。     

Synthesis and Characterization of Polyamides Based on s-Triazine Moiety

Seven polyamides containing s-triazine rings in the main chain were synthesized by high temperature polycondensation of 2-(β-naphthylamino)-4,6-bis(naphthoxy-3-carbonyl chloride)-s-triazine [NANCCT] with various aromatic diamines such as 4,4′-diaminodiphenyl [DADP], 4,4′-diaminodiphenylamide [DADPA], 4,4′-diaminodiphenylsulphone [DADPS], 4,4′-diaminodiphenylsulphonamide [DADPSA], 4,4′-diaminodiphenyl methane [DADPM], 2,4-diamino toluene [DAT] and p-phenylene diamine [PPDA]. All the polyamides were characterized by solubility tests, density measurements, viscosity measurements, IR spectra, NMR spectra, and thermogravimetric analysis. The polyamides had inherent viscosities in the range 0.88–1.16 g/dL in N,N′-dimethyl formamide at room temperature (30°C). All the polyamides showed good thermal stability at high temperatures and most of them were soluble readily at room temperature in polar solvents.     

Polyaramides containing arylene sulfone ether linkages

Polyamides containing arylene sulfone ether linkages were synthesized from 4,4′[sulfonybis (p-phenyleneoxy)] dibenzoyl chloride (SPCI), 3,3′-[sulfonylbis (p-phenyleneoxy)] dibenzoyl chloride (SMCl) and various aromatic diamines (ARD), by solution and interfacial polymerization techniques. In solution polymerization, the effect of various acid acceptors such as propylene oxide (PO), lithium hydroxide (LiOH) in the presence of lithium chloride (LiCl), and triethylamine (TEA) on teh molecular weight of the olyamides was studied. The effect of structure of studied. The effect of structur of various aromatic diamine sof molecular weight and thermal properties of polyamides was also studied. The polyamides prepared were characterized by solution viscosity, elemental analysis thermo-gravimetric analysis, differential scanning calorimetry, and x-ray diffraction. Physical and thermal properties of polyamides prepared from SPcl and Ard were compared with the polyamides prepared from SMCl and ARD.     

A new rigid rodlike colored poly(amide hydrazide): Thermal,optical anisotropic,and mechanical behavior

A new aromatic all-para oriented poly(amide hydrazide) containing an azo group in the main chain was prepared by reacting a symmetric diamine containing a preformed hydrazide group, viz., N,N′-bis(4-aminobenzoyl)hydrazine (BABH), with 4,4′-azobenzoyl chloride (ADBC). The thermal behavior of the polymer was studied by TGA and DSC in air and nitrogen. Films of the polymer were prepared by two processes, viz., wet and dry processes, by using its solution in DMAc containing LiCl. The optical anisotropy, surface morphology, and tensile properties of the films were studied. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1211–1215, 1997     

Preparation of polyamides via the phosphorylation reaction. II. Modification of wholly aromatic polyamides with trifunctional monomers

The trifunctional monomers trimesic acid (TMA) and 3,5-diaminobenzoic acid (DAB), each separately and in combination, were used in amounts of 2 to 5 mole-% in order to increase the molecular weight of aromatic polyamides prepared via the Yamazaki phosphorylation reaction. In general, under comparable conditions the use of DAB led to polymer having higher inherent viscosity (IV) values than did TMA. A typical polymer was the polyisophthalamide of 4,4′-methylenedianiline, MDA-I, prepared by the reaction at 100°C of 4,4′-methylenedianiline (MDA) with isophthalic acid (I) in N-methylpyrrolidione (containing 5% dissolved lithium chloride) and employing triphenyl phosphite as condensation agent with pyridine as catalyst. For molar substitutions of 0.0, 2.0, 2.5, and 3.0% of DAB, MDA–I having IV values respectively of 1.1, 1.3, 1.9, and 2.3 was obtained. The latter two samples have IV values in the same range as those obtained for MDA–I prepared from MDA and isophthaloyl chloride in dimethylacetamide (DMAc) via the low-temperature polycondensation method, which prior experience has shown yields polymers that are quite suitable for the spinning of good fibers. At 5 mole-% substitution of DAB, an IV of 3.7 was obtained but a large quantity of gel particles was observed on dissolving the sample in DMAc containing 5% LiCl, indicating that considerable crosslinking had probably occurred. The rod-like polymer poly-p-benzamide (PPB) was prepared in similar fashion to MDA-I from p-aminobenzoic acid and IV values of respectively 1.6, 2.3, 3.8, and 3.9 were obtained when 0.0, 2.0, 2.5, and 3.0 mole-% of mixed trifunctional monomers were present. A solution of the latter sample dissolved in concentrated sulfuric acid contained considerable gel, indicating that crosslinked polymer was probably produced. It would appear that the chain branching approach for producing high molecular weight PPB for spinning to fibers will not prove useful because PPB having an IV value of about 3 to 4 is considered only marginal for the production of commercial-quality fibers (even though PPB of IV value 1.6 can be spun to high-strength/high-modulus fibers) and because the requisite balance of strength and modulus to elongation to break are only obtained for fibers from PPB having an IV value above about 3.5, and preferably about 5 to 6.     

Preparation and pervaporation performance of 3,3‐bis[4‐(4‐aminophenoxy)phenyl] phthalide based polyimide membranes

A series of novel solvent‐soluble polyimides based on the diamine of 3,3‐bis[4‐(4‐aminophenoxy)phenyl] phthalide (BAPP) were prepared. The effects of the dianhydride structures on the pervaporation performance of aqueous alcohol mixtures through these polyimide membranes were studied. The BAPP‐based polyimide membranes exhibited water permselectivity during all process runs. The permeation rate increased with the addition of bulky groups to the polyimide backbone. The effects of the feed solution concentration, feed solution temperature, and carbon atom number of the feed alcohol on the pervaporation performance were also investigated systematically. Optimum pervaporation results, a separation factor of 22 and a permeation rate of 270 g/m² h, were obtained for a 90 wt % feed aqueous ethanol solution through a 3,3′,4,4′‐biphenyl tetracarboxylic dianhydride polyimide membrane at 25°C. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2046–2052, 2005     

Aromatic polyamides with imide pendent groups

Aromatic polyamides with imide pendent groups were prepared from 4,4′-diaminodiphenylether and imide-diacid chlorides by solution polycondensation. Imidediacid chlorides used included the diacid chlorides of 5-maleimidoisophthalic, 5-dichloromaleimidoisophthalic, 5-tetrahydrophthalimidoisophthalic, 5-chlorendimidoisophthalic, 5-nadimidoisophthalic, 5-methylnadimidoisophthalic and 5-phthalimidoisophthalic acid. The pure aromatic polyamide from 4,4′-diaminodiphenylether and isophthaloyl chloride was also prepared for comparative reasons. Polyamide-imides are soluble in polar organic solvents and show good thermal resistance. They are film-forming and the films have good mechanical properties. Those polyamide-imides which contain unsaturated carbon-carbon bonds may be crosslinked by heating to 220°C, giving rise to insoluble materials with improved mechanical resistance.     

Film studies of certain new aromatic–aliphatic polyamides

Two new aromatic–aliphatic polyamides containing azo linkage in the main chain based on 2,2′‐dimethyl‐4,4′‐diaminoazobenzene and adipic/2‐chloro‐5‐methyl‐1,2‐dioic acid (α‐chloro‐δ‐methyl adipic acid) were synthesized and analyzed by thermogravimetry and films were cast. Also three polymers obtained from condensation of 4,4′‐azodibenzoic acid/adipic acid and 2,2′‐bis [4‐(p‐amino phenoxy) phenyl] propane/4,4′‐diaminoazobenzene were studied in terms of mechanical and morphological properties. Film studies were carried out interms of tensile property, scanning electron microscope, dielectric, microwave, and X‐ray diffraction pattern. Thermal studies have been done using thermogravimetric analysis, differential thermal analysis, and pyrolysis‐mass spectral data. The results were correlated with structure and orientation of the molecules. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1305–1316, 2004     

Synthesis and Characterisation of Polyamides and Polyimides from Amino/Methylene bis[Benzenamine] Styryl Pyridines

Polyamides and polyimides containing diamines, with potential non-linear optical characteristics, were prepared using (E)-4,4′-[[[2-(4-pyridinyl)ethenyl]phenyl]amino]bis[benzenamine] and (E)-4-4′-[[[2-(4-pyridinyl)ethenyl]2-methyl phenyl]amino]bis[benzenamine] condensed with pyromellitic dianhydride to obtain poly(amic acid)s. The poly(amic acid)s were soluble in polar aprotic solvents, such as dimethylformamide, dimethylsulphoxide and dimethylacetamide, and could be cast into transparent, tough, flexible films. Amorphous thermally stable polyimides were formed by cyclodehydration. Similarly, (E)-4,4′-[[[2-(4-pyridinyl)ethenyl]phenyl]methylene]bis[benzenamine] and (E)-4,4′-[[[2-(4-pyridinyl)ethenyl]phenyl]methylene]bis[N-ethylbenzenamine] were condensed with 3-methyladipoyl chloride to obtain other new polyamides. Characterisation using infra-red and nuclear magnetic resonance spectroscopy, X-ray diffraction and thermogravimetric analysis are reported. © 1997 SCI.     

Fabrication and characterization of silica modified polyimide–zeolite mixed matrix membranes for gas separation properties

In this study, new monomers having silica groups were synthesized as an intermediate for the preparation of poly(imide siloxane)-zeolite 4A and 13X mixed matrix membranes (MMMs). The effects of membrane preparation steps, zeolite loading, precursor’s composition, and pore size of zeolite on the gas separation performance of these mixed matrix membranes were studied. The new diamine monomer was prepared from 3,5-diaminobenzoic acid (3,5-DABA), 3-aminopropyltrimethoxysilane (3-APTMS), and zeolite 4A and zeolite 13X in N-methyl-2-pyrollidone (NMP) at 180 °C. Poly(imide siloxane)-zeolite 4A and 13X MMMs were synthesized from pyromellitic dianhydride (PMDA) and 4,4-oxydianiline (ODA) in NMP using a two-step thermal imidization. SEM images of the MMMs show the interface between polymer and zeolite phases getting closer when surface modified zeolite is used. The increase in glass transition temperature (T _g) confirms the polymer chain becoming more rigid induced by the presence of zeolite. The experimental results indicated that a higher zeolite loading resulted in a decrease in gas permeability and an increase in gas pair selectivity. In terms of O₂ and N₂ permeance and ideal selectivity, the separation performances of poly(imide siloxane)-zeolite MMMs were related to the zeolite type and zeolite pore dimension.     

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     

Thorium Ions Transport across Tri-n-butyl Phosphate—Benzene Based Supported Liquid Membranes

Abstract

Transport of Th(IV) ions across tri-n-butyl phosphate (TBP) benzene based liquid membranes supported in microporous hydrophobic polypropylene film (MHPF) has been studied. Various parameters such as variation of nitric acid concentration in the feed, TBP concentration in the membrane, and temperature on the given metal ions transport have been investigated. The effects of nitric acid and TBP concentrations on the distribution coefficient were also studied, and the data obtained were used to determine the Th ions—TBP complex diffusion coefficient in the membrane. Permeability coefficients of Th(IV) ions were also determined as a function of the TBP and nitric acid concentrations. The optimal conditions for the transport of Th(IV) ions across the membrane are 6 mol·dm^?3 HNO₃ concentration, 2.188 mol·dm^?3 TBP concentration, and 25°C. The stoichiometry of the chemical species involved in chemical reaction during the transport of Th(IV) ions has also been studied.     

Polysiloxaneimide membranes for removal of VOCs from water by pervaporation

For the separation of volatile organic compounds (VOCs) from water by pervaporation, three polysiloxaneimide (PSI) membranes were prepared by polycondensation of three aromatic dianhydrides of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (BTDA), and pyromellitic dianhydride (PMDA) with a siloxane‐containing diamine. The PSI membranes were characterized using ¹H‐NMR, ATR/IR, DSC, XRD, and a Rame‐Hart goniometer for contact angles. The degrees of sorption and sorption selectivity of the PSI membranes for pure organic compounds and organic aqueous solutions were investigated. The pervaporation properties of the PSI membrane were investigated in connection with the nature of organic aqueous solutions. The effects of feed concentration, feed temperature, permeate pressure, and membrane thickness on pervaporation performance were also investigated. The PSI membranes prepared have high pervaporation selectivity and permeation flux towards hydrophobic organic compounds. The PSI membranes with 150‐μm thickness exhibit a high pervaporation selectivity of 6000–9000 and a high permeation flux of 0.031–0.047 kg/m² h for 0.05 wt % of the toluene/water mixture. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2691–2702, 2000     

Synthesis and characterization of new polyamides containing p‐phenylenediacryloyl moieties in the main chain

Six new polyamides 8a–f containing p‐phenylenediacryloyl moieties in the main chain were prepared by the direct polycondensation reaction of bis(p‐amidobenzoic acid)‐p‐phenylene diacrylic acid 6 with 1,4‐diphenylene diamine 7a , 1,3‐diamino toluene 7b , 1,5‐diamino naphthalene 7c , 4,4′‐diamino diphenyl ether 7d , 4,4′‐diamino diphenyl sulfone 7e , and 3,3′‐diamino diphenylsulfone 7f by using thionyl chloride, N‐methyl‐2‐pyrolidone, and pyridine as condensing agents. These new polymers 8a–f were obtained in high yield and inherent viscosity between 0.35–0.65 dL/g. The resulting polyamides were characterized by elemental analysis, viscosity measurements, thermal gravimetric analysis (TGA and DTG), solubility test, FTIR and UV–vis spectroscopy. Diacid acid 6 as a new monomer containing p‐phenylenediacryloyl moiety was synthesized by using a three‐step reaction. First, p‐phenylenediacrylic acid 3 was prepared by reaction of terephthal aldehyde 1 with malonic acid 2 in the presence of pyridine, then diacid 3 was converted to p‐phenylenediacryloyl chloride 4 by reaction with thionyl chloride. Finally, bis(p‐amidobenzoic acid)‐p‐phenylene diacrylic acid 6 was prepared by the condensation reaction of phenylenediacryloyl chloride 4 with p‐aminobenzoic acid 5 . © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and the magnetic properties of novel metal(II) complexes of polyamides

Novel polyamides DTPA and DTPyA are prepared from 2,2′-diamino-4,4′-bisthiazole and aromatic polycarbonyl chloride. The complexes of Fe(II) and Cu(II) metal of the polyamides are also prepared. The complexes as well as the polyamides are characterized through IR and EPR, and the magnetic property of each complex are measured through MPMS. It is found the Fe(II) complexes of both DTPA and DTPyA reveal magnetization ability, especially the Fe(II) DTPA complex. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 818–822, 2001