Synthesis and characterization of aromatic–aliphatic polyamides

A new monomer, 2,5‐bis(4‐carboxy methylene phenyl)‐3,4‐diphenyl thiophene (V) has been synthesized and characterized by physical and spectroscopic methods. A series of eight aromatic–aliphatic polyamides was prepared from the (V) and different aromatic diamines using Yamazaki's direct phosphorylation reaction. The polyamides were characterized by IR spectroscopy, viscosity measurements, and thermal analysis. An excellent yield of these polyamides was obtained, with inherent viscosities in the range of 0.28 to 0.67 dL/g, and the polyamide were readily soluble in aprotic polar solvents such as N‐methyl‐2‐pyrrolidone, N‐N‐dimethyl acetamide, dimethyl sulphoxide, and so forth. Polyamides could be cast into transparent and flexible films. They had glass‐transition temperatures of 225–273°C. When evaluated by thermogravimetry, thermal analysis of the polyamides showed no weight loss below 311°C, and the char yield in air at 900°C was 55%–67%. The structure–property correlation among these polyamides is also discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 566–571, 2001     

Synthesis and properties of multiblock copolymers based on polydimethylsiloxane and piperazine-aromatic polyamides

Polydimethylsiloxane (PDMS)–polyamide multiblock copolymers were synthesized by three different methods, i.e., two-step low-temperature solution polycondensation, one-step solution polycondensation, and interfacial polycondensation. In the two-step method, α,ω-diacid chlorideterminated polyamide oligomers were prepared from trans-2,5-dimethylpiperazine (DMP) and terepthaloyl chloride (TPC) or isophthaloyl chloride (IPC) in chloroform in the presence of triethylamine, which in turn were subjected to reaction with α,ω-bis (3-aminopropyl) polydimethylsiloxane (PDMS–diamine) in the same solvent to from multiblock copolymers. In the one-step method, the reaction components, DMP, TPC (or IPC), and PDMS–diamine, were reacted altogether in chloroform in the presence of triethylamine. In the interfacial method, the reaction components were also reacted altogether in an aqueous sodium hydroxide–chloroform two-phase system. These polycondensations afforded the multiblock copolymers having inherent viscosities of 0.1–1.3 dL g^?1 in m-cresol. The PDMS–polyamide multiblock copolymers dissolved in formic acid and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), and transparent, ductile, and elastomeric films were obtained by casting from the HFIP solutions. The films of the multiblock copolymers prepared by three different methods exhibited similar properties by means of thermal analysis and tensile measurements. In the multiblock copolymers, the tensile strength and modulus of the films decreased with increasing the PDMS content, whereas the elongation at break increased.     

Crosslinkable polyamide–imides

A series of polyamide–imides were prepared from aromatic diamines and substituted isophthaloyl chlorides containing unsaturated imide rings. Aromatic polyamides from isophthaloyl chloride were also prepared for comparison. The polyamide-imides gave enhanced solubility compared to the aromatic polyamides and there was no deterioration in thermal stability or T_g. The PAIs were crosslinked by heating at 280°C/4 h under nitrogen. After this heat treatment all the PAIs became insoluble and their mechanical properties increased substantially; their thermal behavior, as measured by DSC and TGA, changed as a function of their chemical structure.     

Synthesis of a novel aromatic–aliphatic hyperbranched polyamide and its application in piezoelectric immunosensors

An aromatic–aliphatic AB₂ monomer, 5‐[3‐(4‐aminophenyl)propionylamino]isophthalic acid, prepared from 5‐aminoisophthalic acid and 3‐(4‐nitrophenyl)propionic acid, and the corresponding hyperbranched polyamide were fabricated. Applications in piezoelectric immunosensors as supports for antibody immobilization were studied. The introduction of the hyperbranched polyamide greatly increased the amount of immobilized antibody on the electrode and consequently increased the sensitivity of the complete piezoelectric immunosensor. The investigation of the properties of the sensors indicated that the hyperbranched polyamide was a suitable support for antibody/antigen immobilization. Copyright © 2007 Society of Chemical Industry     

Assessment of random aromatic co‐polyamides containing two different bulky pendant groups

This work reports the synthesis and assessment of random aromatic co‐polyamides containing two different bulky pendant groups. The random aromatic co‐polyamides are synthesized combining the monomers 5‐tert‐butylisophthalic acid and 5‐(9,10‐dihydro‐9,10‐ethanoanthracene‐11,12‐dicarboximido)isophthalic acid with three different diamines. The random aromatic co‐polyamides are readily soluble and possess inherent viscosities in the range of 0.47–0.60 dL g⁻¹. Co‐polyamide dense membranes are amorphous, and flexible with both good tensile strength (56.2–57.5 MPa) and tensile modulus (1.3–1.6 GPa). Permeability coefficients of the co‐polyamide dense membranes are assessed for the gases He, O₂, N₂, CH₄, and CO₂. It is found that the combination of two bulky pendant groups, dibenzobarrelene and tert‐butyl, in the backbone of the co‐polyamides improves the gas permeability coefficient in comparison with their corresponding homopolyamides. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45884.     

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     

Synthesis of poly(phenylene oxide) — aromatic polyester multiblock copolymers

Summary Poly(phenylene oxide) (PPO) — aromatic polyester multiblock copolymers were synthesized by polycondensation of bisphenol-A / isophthalic acid or m- and p-hydroxybenzoic acids in the presence of PPO having a carboxylic acid at one end and a phenolic hydroxy group at the other using triphenylphosphine / hexachloroethane as coupling agent. TG analysis showed that the multiblock copolymer showed relatively high thermal stability. Received: 5 January 1998/Accepted: 4 February 1998     

Synthesis and properties of polyamides and copolyamides based on 2,6-naphthalene dicarboxylic acid

A number of polyamides based on 2,6-naphthalene dicarboxylic acid (NDA) and various aromatic diamines were synthesized in N-methyl pyrrolidone (NMP) containing lithium chloride (LiCl) or calcium chloride (CaCl₂) by direct polycondensation using triphenyl phosphite and pyridine. The best reaction conditions for polycondensation were determined in terms of factors such as the amount of the solvency-promoting reagent such as LiCl or CaCl₂ and the initial reactant concentration. Thus, almost all polyamides were obtained with inherent viscosities above 1.0 and up to 3.28 dL/g. Similarly, high molecular weight copolyamides with inherent viscosities of 1.76–3.61 dL/g were prepared from 4,4′-oxydianiline (ODA) and mixed dicarboxylic acids of NDA/terephthalic acid (TPA) or NDA/isophthalic acid (IPA). The solubility of NDA homopolyamides depended on the diamine components. The polyamides derived from meta-, sulfone-, or alkylene-linked diamine showed increased solubility. Copolymerization of ODA with NDA/IPA led to a significant increase in solubility, whereas with NDA/TPA, it gave a limited improvement. All the homopolyamides and copolyamides showed an amorphous X-ray diffraction pattern. Almost all the polymers soluble in aprotic solvents can be solution-cast into strong and tough films. Glass transition shifts of some NDA polyamides can be observed in the differential scanning calorimetry (DSC) curves ranging from 243 to 345°C. Most NDA/IPA–ODA copolyamides also showed clear transitions in the range of 255–268°C. In nitrogen, all the polymers showed no significant weight loss up to 400°C, and their 10% weight loss temperatures were recorded in the range of 434–541°C. © 1994 John Wiley & Sons, Inc.     

Maintaining hydrostatic conditions during solidification of polymers in a high-pressure dilatometer

Amorphous polyarylates derived from 12–50 mol % of a t-butyl-substituted diacid, e.g., 5-t-butylisophthalic acid, exhibit miscibility with the amorphous phase of polyamides having aromatic and aliphatic character. Equally critical to blend miscibility is the aliphatic/aromatic carbon atom ratio (exclusive of the amide functionality) of the polyamide. An aliphatic/aromatic carbon atom ratio (α) greater than 1.4 but less than 2.5 is necessary. © 1992 John Wiley & Sons, Inc.     

Facile Synthesis of Ferrocene-Based Polyamides and Their Organic Analogues Terpolyamides: Influence of Aliphatic and Aromatic Sequences on Physico-Chemical Characteristics

Efforts have been devoted to synthesize and characterize processable polymers with desired properties. Herein, four different series of aromatic and aliphatic terpolyamides were prepared via solution phase polycondensation of 4,4′-oxydianiline and hexamethylenediamine (HMDA) with various diacids chlorides (isophthalyol dichloride, terepthalyol dichloride, 1, 1′-ferrocene dicarboxylic acid chloride and trans-azobenzene-4, 4′-dicarbonyl chloride). The structural, morphological and physico-chemical nature of as prepared polymers was explored by Fourier-transform infrared spectroscopy, scanning electron microscopy, thermal analysis (TGA and DSC), and wide-angle x-ray diffraction. Moreover, an aliphatic diamine was incorporated in varying concentration as a flexible methylene spacer and the effect of its concentration on the properties of polyamides was also studied. Changes in various physico-chemical properties such as solubility, inherent viscosity, surface morphology and flame retarding behaviour were investigated. Marked difference in morphology and solubility was observed with the change in the ratio of segments in the chain. Inherent viscosities of polymers ranged from 1.8052–1.6274 dl/g indicating reasonably moderate molecular weights. Interestingly, ferrocene based aromatic polymers were more thermally stable (T_g 260 °C, T_i 310 °C, T_h 525 °C, T_f 720 °C, for PF₀), and also found to exhibit best flame retarding behavior (limiting oxygen index value for PF₀is LOI 33.15%).

     

Study on the preparation and properties of novel block copolymeric materials based on structurally modified organometallic as well as organic polyamides and polydimethylsiloxane

Some novel ferrocene‐containing polyamide‐based block copolymer materials with telechelic polydimethylsiloxane oligomer and their organic analogues were prepared by solution‐phase polycondensation of ferrocene‐based organometallic and terephthaloyl‐ as well as isophthaloyl‐based organic acyl chlorides with a series of semi‐aromatic diamines having ether linkages together with variable aliphatic character. The corresponding polyamides of the synthesized materials, without polydimethylsiloxane segment, were also prepared for comparison of physicochemical properties. None of the synthesized organometallic and organic block copolymers along with their respective polyamides melted below 300 °C and their structural features were confirmed by their physical properties and spectroscopic studies. The weight‐average molecular weights and molecular parameters of all these materials were determined by the static laser light scattering technique. The materials were soluble in sulfuric acid and partially soluble in common organic solvents, and yet became readily soluble upon N‐trifluoroacetylation. The synthesized materials were further characterized by their water absorption characteristics, X‐ray diffraction studies and surface morphology (SEM and AFM) and thermal (DSC and TG) analyses, and their structure–property relationships were elucidated from these studies. The energies of pyrolysis for these materials were calculated by the Horowitz and Metzger method. © 2012 Society of Chemical Industry     

Synthesis and characterization of polyamides and poly(amide‐imide)s derived from 2,6‐bis(3‐aminophenoxy)benzonitrile or 2,6‐bis(4‐aminophenoxy)benzonitrile

A series of polyamides and poly(amide‐imide)s was prepared by direct polycondensation of ether and nitrile group containing aromatic diamines with aromatic dicarboxylic acids and bis(carboxyphthalimide)s respectively in N‐methyl 2‐pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. New diamines, such as 2,6‐bis(4‐aminophenoxy)benzonitrile and 2,6‐bis(3‐aminophenoxy)benzonitrile, were prepared from 2,6‐dichlorobenzonitrile with 4‐aminophenol and 3‐aminophenol, respectively, in NMP using potassium carbonate. Bis(carboxyphthalimide)s were prepared from the reaction of trimellitic anhydride with various aromatic diamines in N,N′‐dimethyl formamide. The inherent viscosities of the resulting polymers were in the range of 0.27 to 0.93 dl g^?1 in NMP and the glass transition temperatures were between 175 and 298 °C. All polymers were soluble in dipolar aprotic solvents such as dimethylsulfoxide, dimethylacetamide and NMP. All polymers were stable up to 350 °C with a char yield of above 40 % at 900 °C in nitrogen atmosphere. All polymers were found to be amorphous except the polyamide derived from isophthalic acid and the poly(amide‐imide)s derived from diaminodiphenylether and diaminobenzophenone based bis(carboxyphthalimide)s. Copyright © 2004 Society of Chemical Industry     

N-Propargyl-substituted aromatic polyamides: preparation and thermal crosslinking

A series of high molecular weight aromatic polyamide copolymers derived from 4,4′-bis(methylamino)-diphenylmethane, 4,4′-bis(propargylamino)diphenylmethane and isophthaloyl dichloride was prepared as potential candidates for use as matrix resins in Kevlar^(R) fibre composites. These polyamides, which contain pendant propargyl groups, underwent facile crosslinking at 280°C as evidenced by dramatic increases in their glass transition temperatures (T_g) and accompanying loss of solubility. Other attempts to effect crosslinking by exposure to ultraviolet light, electron beam or gamma radiation were unsuccessful.     

Thermal characterization of butadiene–isoprene copolymers with a 1,2/3,4 structure

Two series of butadiene–isoprene copolymers with a 1,2 and/or 3,4 structure were prepared at different polymerization temperatures, using CrCl₂(dmpe)₂‐MAO as a catalyst system. Copolymerization carried out at higher temperature resulted in polymers in the whole range of monomeric ratio, from the highly crystalline 1,2‐syndiotactic polybutadiene to the amorphous 3,4‐polyisoprene. The molar composition of the butadiene–isoprene copolymers and the syndiotactic index of the butadiene sequences, represented as molar fraction of the syndiotactic pentads, were evaluated by carbon‐13 nuclear magnetic resonance spectroscopy. The thermal behavior of the copolymers was investigated by differential scanning calorimetry. Nonisothermal crystallization kinetics were characterized by Ziabicki and Avrami methods as modified by Jeziorny. The crystallization and melting temperatures and the enthalpy of fusion of the copolymers were in good correlation with the syndiotactic index of butadiene sequences. The index was influenced by polymerization temperature and composition of butadiene–isoprene copolymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 12: 2737–2743, 2003     

Miscible blends of styrene-acrylic acid copolymers with aliphatic,crystalline polyamides

Styrene-acrylic acid copolymers exhibit miscibility with various aliphatic, crystalline polyamides (e.g., nylon 6, 11, and 12) at 20% acrylic acid content in the copolymer. At 8% acrylic acid, phase separation is observed with the crystalline polyamides. At 14% acrylic acid, partial miscibility is observed with each polyamide, resulting in the T_g's of the constituents shifted toward the other constituent. The miscibility of the styrene-acrylic acid copolymers ( > 14 wt % AA) can be ascribed to hydrogen bonding interactions with the polyamides. Styrene-acrylic acid (20% AA) copolymers are miscible with other nylons with alternating amide orientation along the chain (e.g., nylon 6,6 and nylon 6,9). These samples tend to crosslink upon exposure to temperatures above the polyamide melting point unlike the nylon 6, 11, and 12 blends in which branching may only occur. Nylon 11/styrene-acrylic acid blends were chosen for crystallization rate studies. A melting point depression of nylon 11 occurs with addition of the styrene-acrylic acid (20% AA). The Flory-Huggins interaction parameter from the melting point depression is calculated to be -0.27. The crystallization rate of nylon 11 is significantly reduced with the addition of the miscible SAA copolymers (20% AA). The spherulitic growth rate equation predicts this behavior based on a T_g increase with SAA addition.     

The effect of furan molecular units on the glass transition and thermal degradation temperatures of polyamides

Interfacial polymerization is used to prepare biobased furan polyamides from the carbohydrate‐derived monomer, 2,5‐furan dicarboxylic acid, aromatic diamines, and varying chain length aliphatic diamines. The molecular weights of the furan polyamides variations range 10,000–70,000 g/mol. These biobased polyamides have improved solubility relative to petroleum‐derived polyamides affording enhanced processability options. The glass transition temperatures (T_g) of the biobased furan polyamides are higher than that of aliphatic analogs, but lower than phenyl‐aromatic analogs. The T_g for these furan polyamides are as high as 280 °C. Also, the furan polyamide glass transition temperatures increase with decreasing aliphatic diamine chain length similar to results exemplified in petroleum‐based nylons. Group contribution parameters are determined for furans to enable simple prediction of the glass transition temperature and decomposition temperature of furan polyamides. The molar glass transition function for the furan is calculated to be 27.6 ± 1.5 K kg/mol. Thermal analysis measurements of the biobased furan polyamides have maximum thermal degradation temperatures at 350 °C or higher, similar to that of aliphatic polyamides when scaled with the number average molecular weight. The molar decomposition temperature functions are determined to be 37 K kg/mol for furans bonded to aliphatic units and 42 K kg/mol for furans bonded to phenyl units. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45514.     

A synthesized semi-aromatic copolyamaide through synergy of three different kinds of monomers: Toward high transparency,excellent heat resistance and melt flowing property

To fabricate the low-cost transparent polyamide with high heat resistance and good melt flowing property simultaneously is a huge challenge in many high-end fields due to the contradiction between these two properties. In order to balance this contradiction, in this paper, by using isophthalic acid (IPA, aromatic monomer), 4,4′-methylenebis(cyclohexylamine) (PACM, alicyclic monomer) as rigid stereoscopic monomers, 1,6-hexanediamine (HMD, aliphatic monomer) as the flexible monomer, a series of transparent poly(hexamethylene isophthalamide/poly(m-benzoyl4,4′-methylenebis(cyclohexylamine)) (PA6I/PACMI) with rigid and stereoscopic structure (corresponding to the large distance between adjacent molecular chains) were successfully synthesized. The results indicated that the newly synthesized PA6I/PACMI copolymer has an intrinsically amorphous structure and high optical transparency, which could reach as high as 90%. Furthermore, the highest glass transition temperature (T_g) of the copolymer is over 153.9°C, at the same time, the copolymer also possesses excellent melt flowing property, which can be melt processed easily. Therefore, the newly synthesized copolymer has great advantages in many fields, and it can also shed light on the design and fabrication of high-performance materials.     

Synthesis and properties of novel aromatic polyamides derived from 2,2‐bis[4‐(4‐amino‐2‐fluorophenoxy) phenyl]hexafluoropropane and aromatic dicarboxylic acids

A series of polyamides were synthesized by the direct polycondensation of 2,2‐bis[4‐(4‐amino‐2‐fluorophenoxy)phenyl]hexafluoropropane with various commercially available dicarboxylic acids such as terephthalic acid, isophthalic acid, 5‐t‐butyl isophthalic acid, and 2,6‐naphthalene dicarboxylic acid. The synthesized polyamides were soluble in several organic solvents such as N,N‐dimethylformamide, N,N‐dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, and chloroform, and they exhibited inherent viscosities of 0.42–0.59 dL/g. The polyamides exhibited weight‐average molecular weights of up to 26,000, which depended on the exact repeating unit structure. These polyamides showed good thermal stability up to 440°C for a 10% weight loss in synthetic air. The polyamides synthesized from 5‐t‐butyl isophthalic acid and isophthalic acid exhibited glass‐transition temperatures of 217 and 185°C, respectively (by differential scanning calorimetry) in nitrogen. The polyamides synthesized from terephthalic acid and 2,6‐naphthalene dicarboxylic acid showed melting temperatures of 319 and 385°C, respectively. The polyamides films were pale yellow, with tensile strengths of up to 82 MPa, moduli of elasticity of up to 2.3 GPa, and elongations at break of up to 9%, which depended on the exact repeating unit structure. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 691–696, 2003     

Thermal behavior of aliphatic–aromatic poly(ether-amide)s

The thermal properties of a set of experimental aliphatic–aromatic polyamides containing ether linkages were examined as a function of their chemical structure. Variations of the glass transition temperature (T_g) and melting temperature (T_m) could be correlated with the length of the aliphatic spacers and with the orientation of the phenylene rings. Polymers with a high concentration of p-oriented phenylene units showed a higher T_g than those containing mainly m-oriented ones; T_g values ranged from 110 to 155°C. Surprisingly, a negligible dependence of T_gs on the nature of flexible spacers was observed. For all of the polymers, the thermal stability was virtually the same, about 440°C, when tested by dynamic thermogravimetric analysis (TGA). However, quite different levels of thermal stability were found by isothermal TGA analysis for polyamides with different flexible spacers. Moreover, the poly(ether-amide)s described here compare fairly well with wholly aromatic polyamides when measured by dynamic TGA; but isothermal TGA measurements clearly demonstrated that they decompose faster than aromatic polyamides. Treatment of the TGA curves by the method of McCallum provided kinetic data that confirmed a better long-term stability for poly(ether-amide)s with a higher proportion of para-oriented phenylene rings. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:975–981, 1998     

A simple and efficient way to synthesize optically active polyamides by solution polycondensation of di‐O‐methyl‐L‐tartaryl chloride with diamines

A series of optically active polyamides containing di‐O‐methyl‐L ‐tartaryl moieties in the main chain were synthesized by polycondensation of di‐O‐methyl‐L ‐tartaryl chloride 5 with diamines and characterized by gel permeation chromatography, UV–vis, circular dichroism (CD), IR, and NMR spectroscopies. The polycondensation reaction could be carried out under mild conditions and the reaction time was short (2–3 h). The key monomer 5 prepared from L ‐tartaric acid via esterification, etherification, hydrolysis, and chlorination was easily purified by vacuum sublimation. These polyamides with number average molecular weights ranging from 14,000 to 35,000, displayed large optical activity in dimethyl sulfoxide solution, and their specific optical rotations oscillated between 87.2° and 210.7° depending on the structures of the diamines. The glass transition temperatures of these polyamides were in the range of 106–191°C, and the 10% mass loss occurred at temperature above 300°C. The polyamides derived from aromatic diamines exhibited higher T_g and thermal stability than those derived from aliphatic diamines. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010