Isophthaloyl Chloride Research Articles

Production, characterization, and surface morphology of novel aromatic poly(amide-ester-imide)/functionalized TiO2 nanocomposites via ultrasonication assisted process

New aromatic poly(amide-ester-imide) (PAEI) was prepared by phase transfer-catalyzed interfacial polycondensation of N,N′-(1,3,5,7-tetraoxo-5,7-dihydropyrrolo[3,4-f]isoindole-2,6(1H,3H)-diyl)bis(4 hydroxybenzamide) diol, with isophthaloyl chloride. The resulting PAEI was characterized by inherent viscosity measurements, solubility test, Fourier transform infrared (FT-IR), and 1H-NMR spectroscopy. Then, the PAEI was used as a polymer matrix for the preparation of PEAI/modified TiO2 nanocomposite (NC). In order to improve the dispersion of TiO2 nanoparticles in the polymer matrix, the surface of TiO2 nanoparticles was modified with N,N′-(pyromellitoyl)-bis-l-isoleucine diacid (DA). The obtained PAEI/DA-TiO2 NCs were characterized by FT-IR spectra, X-ray diffraction, field emission scanning electron microscopy, and transmission electron microscopy. Morphology study demonstrated that DA-TiO2 nanoparticles were dispersed homogeneously in the polymer matrix. The thermogravimetric analysis indicated an enhancement of the thermal stability of the NCs via increasing nanoparticles contents.

Controlled sulfonation of poly(arylene ether sulfone)s and poly(arylene ether ketone)s with different molecular structures for polymer electrolyte membranes

ABSTRACTPoly(arylene ether sulfone) copolymers derived from 9,9-bis(4-hydroxyphenyl)fluorene, bisphenol S and 4,4′-difluorodiphenylsulfone and poly(arylene ether ketone) copolymers derived from 4-phenoxybiphenyl, diphenyl ether and isophthaloyl chloride were prepared as precursor polymers for sulfonation reaction in which sulfonic groups are introduced quantitatively into specified positions. Sulfonation reaction for these two series of copolymers by concentrated sulfuric acid was successfully carried out to give sulfonated polymers with controlled positions and degree of sulfonation. Thermal stability, moisture absorption and proton conductivity for these two series of copolymers were measured and the results were compared to those of perfluorosulfonic acid polymers.

Preparation and characterization of new aromatic poly(ether ester)s bearing cardo xanthene groups

A series of new aromatic poly(ether ester)s containing cardo xanthene groups were synthesized by phase transfer–catalyzed interfacial polycondensation of three cardo bisphenols such as 9,9-bis(4-hydroxyphenyl)xanthene, 9,9-bis (4-hydroxy-3-methylphenyl)xanthene, and 9,9-bis(4-hydroxy-3,5-dimethylphenyl)xanthene with terephthaloyl chloride and isophthaloyl chloride. Inherent viscosities and number average molecular weights of the polymers were in the range 0.56–0.80 dL g−1 and 30,300–36,200, respectively. The resulting poly(ether ester)s exhibited high glass transition temperatures ranged from 208°C to 274°C, and their 10% weight loss temperatures were in the range of 440–458°C with char yields above 45% at 600°C under a nitrogen atmosphere. All the poly(ether ester)s were amorphous and readily soluble in organic solvents such as dichloromethane, chloroform, tetrahydrofuran, meta-cresol, pyridine, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidinone at room temperature and could be cast into tough, transparent, and flexible films with tensile strengths of 68.2–86.8 MPa, elongations at break of 2–3%, and tensile moduli of 5.7–7.8 GPa.

Synthesis and characterization of new aromatic polyesters with a (4-phenoxyphenyl)phenylmethene linkage

A series of new aromatic polyesters containing a (4-phenoxyphenyl)phenylmethene linkage were prepared by phase transfer-catalyzed interfacial polycondensation of 1,1-bis(4-hydroxyphenyl)-1-(4-phenoxyphenyl)-1-phenylmethane with terephthaloyl chloride, isophthaloyl chloride, and so on. The inherent viscosities of the polyesters ranged from 0.62 to 0.90 dL/g, while number-average molecular weights were in the range of 30,500–35,500 g/mol. All the polyarylates were readily soluble in organic solvents such as dichloromethane, chloroform (CDCl3), tetrahydrofuran, meta-cresol, pyridine, N, N-dimethylformamide, N, N-dimethylacetamide, and 1-methyl-2-pyrrolidinone at room temperature, and could be cast into tough, transparent, and flexible films from their CDCl3solutions. Wide-angle X-ray diffraction measurements revealed the amorphous nature of the polyarylates. These polymers showed glass transition temperatures ( Tgs) between 178°C and 240°C and decomposition temperatures at 10% weight loss ranging from 446°C to 483°C, while the initial degradation temperatures in the range of 410–435°C under nitrogen atmosphere. These new polyarylates exhibited higher Tgs and better solubility than bisphenol A-based analogues.

Synthesis and thermal properties of polyhydroxyamide copolymer and its derivatives

We synthesized a polyhydroxyamide (PHA) copolymer via low-temperature solution polymerization of 3,3'-dihydroxybenzidine with terephthaloyl chloride (80.0 mol%) and isophthaloyl chloride (20.0 mol%) in N,Ndimethylacetamide with the aid of LiCl. We prepared the PHA copolymer derivatives containing the fluorine-based substituents and investigated their solubility, cyclization behavior, and thermal properties using a differential scanning calorimeter (DSC), a thermogravimetric analyzer (TGA), and the simultaneous thermogravimetric analyzer coupled with a mass spectrometer (STA-MS). The chemical structures of the PHA copolymer and its derivatives, as well as the polybenzoxazoles (PBOs) obtained through thermal cyclization of the copolymer and derivatives, were determined by a fourier transform infrared (FT-IR) spectroscopic analysis. The PHA copolymer could be dissolved in organic solvents only with the aid of LiCl, while its derivatives were readily soluble in DMAc and NMP without LiCl at room temperature. The DSC and TGA results demonstrated that the PHA copolymer derivatives could be converted to PBOs at a lower temperature than the PHA copolymer.

Synthesis of a diacetylene-containing polyisophthalate and its third-order nonlinear optical susceptibility

In order to obtain amorphous thin films of a polydiacetylene, a polyisophthalate containing a push–pull diacetylene chromophore was synthesized by the reaction of p-(N,N-diethanolamino)-p’-nitrodiphenylbutadiyne with isophthaloyl chloride in anhydrous 1-methyl-2-pyrrolidone. The polymer was soluble in organic solvents, such as chloroform, tetrahydrofuran, dimethylformamide, etc., and films with good optical quality were obtained by spin coating from its N-methyl-2-pyrrolidone solution. It was characterized by 1H-NMR, IR, DSC, UV–Visible, X-ray, etc. The diacetylene groups underwent polymerization in the film when irradiated with UV light at 120 °C under Ar atmosphere, and it contained free radicals with a radical concentration of 1016 radicals/g. The third-order nonlinear optical susceptibility, χ(3), of the polymer film measured by the Z-scan technique at 1064 nm was not noticeable, but when the film was heated and irradiated with UV light, a χ(3) value of 6.4 × 10−10 esu was obtained due to increase in π-conjugation by the formation of polydiacetylene in the side chain.

Synthesis and characterization of novel poly(aryl ether ketone)s containing biphenylene moieties and pendant cyano groups

Two monomers, 4,4′-bis(4-phenoxybenzoyl)diphenyl (BPOBDP) and 2,6-diphenoxybenzonitrile (DPOBN), were conveniently prepared via simple synthetic procedures from commercially readily available materials. A series of novel poly(aryl ether ketone)s containing biphenylene moieties and pendant cyano groups were synthesized by the Friedel-Crafts acylation copolycondensation of isophthaloyl chloride (IPC) with a mixture of BPOBDP and DPOBN, over a wide range of BPOBDP/DPOBN molar ratios, in the presence of anhydrous AlCl3 and N-methylpyrrolidone (NMP) in 1,2-dichloroethane (DCE). The copolymers with 10–50 mol% DPOBN are semicrystalline and had higher T gs than those of the conventional PEEK and PEKK due to the incorporation of biphenylene moieties and pendant cyano groups. The copolymer VI with 50 mol% DPOBN had not only high T g of 168 °C, but also moderate T m of 333 °C, having good potential for melt processing. The copolymer VI had tensile strength of 103.4 MPa, Young’s modulus of 2.62 GPa, and elongation at break of 20.7 % and exhibited high thermal stability and excellent resistance to organic solvents.

Modification of hollow fiber ultrafiltration membranes by interfacial polycondensation: Monomer ratio effect

The effect of the component ratio on the permeability and contact angle of ultrafiltration polysulfone hollow fiber membranes modified by interfacial polycondensation of triethylenetetramine (TETA) and isophthaloyl chloride (IPC) has been studied. It has been found that the dependence of the rejection factor on the monomer ratio in the TETA: IPC range from 1: 28 to 20: 1 has two peaks. The first rejection peak is observed in a narrow range of TETA: IPC ratios close to 7: 1. The second peak is observed in a rather broad range of isophthaloyl chloride excess, at TETA: IPC equivalent ratios 1: (5–15). The membrane pure water flux was shown to change conversely to the rejection coefficient. The influence of the average functionality of the system on the change in the selectivity of the modified membranes was studied. A correlation between hydrophilicity and permeability of the modified membranes was revealed: with decreasing contact angle the pure water flux enhances, and the rejection coefficient decreases.

New aromatic polyamides and polyimides having an adamantane bulky group

This paper reports the synthesis and characterization of a new rigid diamine monomer, having a spiro carbon moiety and an adamantane bulky group in its structure; namely spiro-(adamantane-2,9′(2',7'-diamino)-fluorene) (SADAF). After its synthesis, using a straightforward methodology, a novel family of aromatic polyimides (PIs) and polyamides (PAs) has been attained by reaction of SADAF with three aromatic dianhydrides and two diacid chlorides, respectively. Two of the polyimides were obtained through the formation of the corresponding polyamic acid and subsequent thermal cycloimidization, whereas the other one, the polyimide from SADAF and 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), could be synthesized by chemical imidization from the polyamic precursor. Regarding polyamides, two new ones, made from SADAF and isophthaloyl chloride (IPC) and the diacid chloride of 2,2-bis(4-carboxyphenyl) hexafluoropropane (6FC) could be obtained. All the polymers showed high Tg, above 350°C, and excellent thermal resistance, with onset degradation temperatures higher than 450°C. Polymers formed by the combination of SADAF with 6FDA and 6FC were prepared as dense films with good mechanical properties and their permselectivity properties were measured.

Fermentation of aromatic lactate monomer and its polymerization to produce highly thermoresistant bioplastics

Microbial fermentation system is designed to convert glucose to 4-hydroxyphenyllactic acid (DHPA), an aromatic-containing derivatives of lactic acid. By a methylation, DHPA was transformed to a diol monomer to synthesize bio-based polyesters with benzene rings in their backbone. The polycondensation of DHPA diol was performed with a series of aliphatic diacid chlorides to produce semi-aromatic polyesters with glass-transition temperatures <45 °C. By polycondensation with aromatic diacylchlorides such as terephthaloyl chloride and isophthaloyl chloride, thermally stable DHPA-based polyesters with glass-transition temperatures as high as 130 °C were obtained.

Intrinsically colored wholly aromatic polyamides (aramids)

This work describes the preparation of intrinsically blue-colored, high-performance aromatic polyamides (aramids). The color was achieved by preparing a diamine monomer containing a chromogenic azadipyrromethene (ADPM) core, which after polymerizing it with commercially available m-phenyleneisophtahlamide and isophthaloyl chloride gave the blue-colored polyisophthalamide copolymers. These materials were structurally compared to commercialized and high-value-added meta-aramid fibers [poly(m-phenyleneisophthalamide), MPIA, brand names: NOMEX® and Teijinconex®]. Blue is the highest demanded color in the market of protective aramid fibers. The coloration efficiency of this special monomer is very high. Furthermore, the aramids showed even better thermal properties than commercial MPIA.

Rigid‐Rod Polyamides from 3,3′‐bis­(trifluoromethyl)‐4,4′‐diamino‐1,1′‐biphenyl

A diamine monomer with trifluoromethyl groups, 3,3′‐bis(trifluoromethyl)‐4,4′‐diamino‐1,1′‐biphenyl, is synthesized from 5‐bromo‐2‐nitrobenzotrifluoride with two steps. The model reaction with monofunctional benzoyl chloride at room temperature gives the model compound with a quantitative yield. The results of the model reaction indicate that the amine groups have sufficient reactivity in spite of the presence of electron‐withdrawing and bulky trifluoromethyl group at the ortho position. The monomer is polymerized with terephthaloyl chloride and isophthaloyl chloride in N,N‐dimethylacetamide (DMAc) or DMAc containing LiCl using pyridine as an acid acceptor at room temperature. All synthesized polymers are somewhat crystalline and colorless. While the meta‐linked polyamide (PA2) shows excellent solubility in polar aprotic solvents, the para‐linked one (PA1) is dissolved in polar aprotic solvents containing LiCl and concentrated H2SO4. They show good thermal and thermooxidative stability as well as high melting temperatures. image

Control of chain ends of polyesters in polycondensation of AA and BB monomers by use of solid‐phase reagent

ABSTRACTFor selective synthesis of linear polyester having a functional group at one end, polycondensation between 1,4‐butanediol (1a) and sebacoyl chloride (2a) and between 1,12‐dodecanediol (1b) and isophthaloyl chloride (2b) was conducted in the presence of oxime resin or oxime silica gel, followed by cleavage of the formed polyester from the solid‐phase support with aniline. Matrix‐assisted laser desorption ionization time‐of‐flight mass spectra and 1H NMR spectra of the cleaved polyester showed that the products contained not only polyester with anilide at one end (poly 1), but also polyester with anilides at both ends (poly 2). The product ratio of poly 1 to poly 2 (poly 1/poly 2) was dependent on monomers, monomer concentration, feed ratio of monomer to oxime moiety in the support, oxime content in the support, reaction solvent, and the nature of the support. Polyester with a high poly 1/poly 2 ratio of 81/21 and moderate molecular weight (Mn = 1430 g/mol) was obtained by polycondensation of 1b and 2b in the presence of oxime silica gel in dichloromethane. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 1379–1386

Designed polyamides based on 1,4-bis[(4-aminophenyl)-1,3,4-oxadiazolyl]phenylene (BAPO) for removal of Cu(II) and Co(II)

A novel aromatic diamine, 2,5-bis-(aminopyridine-2-yl)-1,3,4-oxadiazole (BAPO), containing two pyridine rings and an 1,3,4-oxadiazole moiety, is synthesized. It is used in a polycondensation polymerization with various aromatic diacid chlorides to generate a series of new aromatic polyamides (PAs). Thermophysical properties of the synthesized PAs are studied by thermogravimetric analysis, differential thermal analysis, dynamic mechanical thermal analysis, and inherent viscosity measurements. The removal of Cu(II) and Co(II) from aqueous solutions is performed using PA 6 that is obtained from BAPO and isophthaloyl chloride. The maximum adsorption capacity is observed at pH 7.0 of about 182.1 mg g−1 that is much greater than that of our previously reported polymer of almost similar structure.

Synthesis and characterization of polyhydroxyamide copolymers as precursors of polybenzoxazoles

Polyhydroxyamide (PHA) and its copolymers were synthesized via low-temperature solution polycondensation of 3,3′-dihydroxybenzidine (DHB) with terephthaloyl chloride (TPC) and/or isophthaloyl chloride (IPC) in N,N-dimethylacetamide (DMAc) with the aid of lithium chloride (LiCl). The synthesized PHA copolymers were characterized by 1H-NMR spectroscopy, FT-IR spectroscopy, and thermogravimetric analyzer (TGA) in order to understand the relations between the chemical structures and the solubility and thermal properties of PHA copolymers. Thermal cyclization of PHA copolymers and the formation of polybenzoxazoles (PBOs) were investigated using FT-IR spectroscopy and TGA. The solubility test revealed that PHA copolymers containing IPC content over 20 mol% were readily dissolved in a variety of polar amide solvents with the aid of LiCl. TGA results showed that the thermal cyclization temperature, the thermal degradation temperatures of PHA copolymers and the thermal stabilities and the char yields of converted PBO copolymers were significantly reduced by the inclusion of meta-structure in the main chain especially when the IPC content was higher than 25 mol%.

Rapid and facile synthesis of a low-cost monolithic polyamide aerogel via sol–gel technology

We report the first synthesis of a good-formability polyamide aerogel using melamine and isophthaloyl chloride via sol–gel technology followed by carbon dioxide supercritical drying. The chemistry employed is straightforward and simple, relying on no catalysts and no nitrogen-based protective atmosphere. The influence of an important factor, temperature, on the aerogels’ structure is briefly discussed and the optimal temperature is 75°C. The aerogels’ structural properties are characterized by the field emission scanning electron microscopy (FESEM), the high resolution transmission electron microscopy (HRTEM) and the Brunauer–Emmett–Teller methods (BET). The results indicate that the aerogel has a typical three-dimensional porous structure with pore diameter about 20nm and the specific surface area can be as high as 282m2/g. Due to the good flame resistance of melamine, the aerogel has potential for use in fireproofing building materials.

Synthesis and properties of poly(aryl ether ketone)s containing both biphenylene moieties and sulfone linkages in the main chain

Two monomers, 4,4′-bis(4-phenoxybenzoyl)biphenyl (BPOBBP) and 4,4′-diphenoxydiphenyl sulfone (DPODPS), were conveniently synthesized via simple synthetic procedures from readily available materials. A series of novel poly(aryl ether ketone)s containing both biphenylene moieties and sulfone linkages in the main chain were synthesized by the modified electrophilic Friedel-Crafts acylation copolycondensation of isophthaloyl chloride (IPC) with a mixture of BPOBBP and DPODPS, over a wide range of BPOBBP/DPODPS molar ratios. The resulting polymers were characterized by Fourier transform infrared spectroscopy (FT-IR), wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA), etc. The results indicated that the copolymers with 30 to 35 mol% DPODPS were semicrystalline and had remarkably increased glass transition temperatures (Tgs) over the conventional poly(ether ether ketone) (PEEK) and poly(ether ketone ketone) (PEKK) due to the incorporation of biphenylene units and sulfone linkages in the main chain. The copolymers with 30 to 35 mol% DPODPS had not only high Tgs of 176 to 177°C, but also moderate melting temperatures (Tms) of 334 to 337°C, having good potential for the melt processing. The semicrystalline copolymers II to V had tensile strengths of 99.8 to 103.1 MPa, Young's moduli of 2.26 to 2.79 GPa, and elongations at break of 16.8 to 26.5% and exhibited outstanding thermal stability and good resistance to organic solvents. POLYM. ENG. SCI., 55:2140–2147, 2015. © 2015 Society of Plastics Engineers

Simultaneous determination of total specific migration limit of seven benzene polycarbonic acids and their derivatives in food simulants by high performance liquid chromatography-ultraviolet detection

A novel method for simultaneous determination of total specific migration limits (SML (T)) of trimellitic, isophthalic, terephthalic, phthalic acid and their derivatives (1, 2, 4-benzenetricarboxylic anhydride, isophthaloyl chloride and terephthaloyl chloride) in food simulants (10% (v/v) ethanol, 20% (v/v) ethanol, 50% (v/v) ethanol, 3% (w/v) acetic acid and olive oil) was developed by high performance liquid chromatography-ultraviolet detection (HPLC-UV). After the migration test, the soaking solution was cooled down and vortexed. After the extraction of olive oil food simulants with 0. 1% (w/v) ammonium acetate aqueous solution, the clear aqueous solution or other aqueous food simulants was filtered through a hydrophilic polytetrafluoroethylene filter with a disposable syringe before injection. The Synergi Polar-RP column (250 mm x 4.6 mm, 4 µm) and gradient elution mode were selected. The variable wavelength detector was set at 232 nm. The limits of quantification were 0.1-0.2 mg/kg; the linearity of the method was good with r2 > 0.999 91 over the range from 0.5 to 12 mg/L for aqueous food simulants or 0.5 to 12 mg/kg for olive oil food simulants. The recoveries of them were between 94. 3% and 105% with the relative standard deviations between 0.1% and 2.3% at the levels of 1.25, 2.50, 6.25 mg/kg. The method shows the low limits of detection, good recoveries and accuracies, and meets the requirement of ( EU) No 10/2011 regulation for the total specific migration limits of trimellitic, isophthalic, terephthalic, phthalic acids and their derivatives. The method has been applied to the analysis of food contact material samples.

Preparation and Properties of Nanocomposites Derived from Aromatic Polyamide and Surface Functionalized Nanoclay

Nanocomposites were synthesized from polyamide and aminosilane functionalized montmorillonite through solution intercalation method. Polyamide resin was prepared by reacting a mixture of p-phenylenediamine and 4,4′-oxydianiline with isophthaloyl chloride (IPC) in N,N′-dimethyl acetamide (DMAc) under anhydrous conditions. The resulting chains were end capped with carbonyl chloride using slight excess of IPC near the end of reaction. 3-Aminopropyltriethoxysilane (APTS) was used for the surface modification of clay. Triethoxysilane groups of APTS promoted the reaction between silane and hydroxyl groups on the surface of clay. The compatibility between the two disparate phases was achieved through interaction of free amine groups of modified clay with carbonyl chloride of the matrix. Thin films obtained by evaporating the solvent were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM), Transmission electron microscopy (TEM), Thermogravimetric analysis (TGA), Differential scanning calorimetry (DSC), and tensile measurements. XRD and TEM results revealed the formation of partially delaminated and intercalated clay platelets in the matrix. Mechanical data showed improvement in the tensile strength and moduli of the nanocomposites with clay loading up to 6 wt.%. The glass transition temperature increased up to 134°C for the nanocomposites containing 6 wt.% clay content and also the thermal stability augmented with increasing clay loading.

Effect ofN-methyl amide linkage on hydrogen bonding behavior and water transport properties of partiallyN-methylated random aromatic copolyamides

The synthesis, conformational preferences, hydrogen bonding behaviors, and membrane properties of new partially N-methylated random aromatic copolyamides were reported. These copolyamides were prepared by the low temperature polycondensations of isophthaloyl chloride with 3,5-diaminobenzoic acid, N,N'-dimethyl-4,4'-diaminodiphenyl ether (MDAE), and 4,4'-diaminodiphenyl ether. The incorporation of the N-methyl amide linkages into the polymer backbone decreased the contents of the cis conformation in the N-methyl amide linkages and suppressed the hydrogen bondings among the amide linkages. Furthermore, the surface hydrophilicity of the copolyamides evaluated by water contact angle measurements decreased with increasing the MDAE unit in the polymer backbone. These experimental results indicated that the suppression of the hydrogen bonding and the existence of the tertiary amide linkage in the cis conformation induced the loose packing of the polymer chains. As a result, the incorporation of the N-methyl amide linkage increased water flux and decreased salt rejection. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 3453–3462