Acylated and hydroxylated polyamides derived from l-tartaric acid

A series of polyamides 6,4 were prepared from 1,6-hexanediamine and active esters of 2,3-di-O-acylated l-tartaric acid by polycondensation in solution. Both O-alkoyl and O-benzoyl esters were used as hydroxyl protecting groups. The resulting acylated polytartaramides were found to be semicrystalline polymers with T_m between 100 and 200 °C and T_g slightly above 100 °C. Controlled hydrolysis of the ester side group led to the preparation of poly(hexamethylene l-tartaramide)s with different content in free hydroxyl groups. These polyamides continue being crystalline but their properties largely differ from those displayed by their parent acylated polymers.     

Polyamide derived from 4,4′-thiobis(methylene)dibenzoyl chloride and aliphatic diamine: interfacial synthesis and characterization

A series of processable semi-aromatic polyamides containing thioether and methylene units were synthesized through the reaction of 4,4′-thiobis(methylene)dibenzoyl chloride and aliphatic diamine by the method of interfacial polycondensation. These polyamides had excellent thermal properties with glass transition temperatures (T _g) of 104.3–130.6 °C, melting temperatures (T _m) of 300.3–303.8 °C, and initial degradation temperatures (T _d) of 405.2–410.3 °C. They had wider processing windows than traditional semi-aromatic polyamides (such as PA6T can not be processed by melting) and can be processed by melting method. They had better tensile strengths of 57.6–64.1 MPa, low-temperature mechanical properties, low water absorption of 0.19–0.27 %, low dielectric constants of 3.11–3.95 at 100 kHz, and better melt flowability properties of 232–60.7, 301.9–78.8, and 423.1–83.6 Pa s under a shear rate ranging from 20 to 1,170 s^?1, respectively. In addition, these polyamides showed good corrosion resistance, they did not dissolve in solvents such as NMP, DMSO, hydrochloric acid (6 mol/l), and solution of NaOH (1 mol/l) and so on.     

Synthesis and characterization of polyamide resins from soy-based dimer acids and different amides

A series of soy-based polyamides with different dimer acids and diamines were synthesized using a condensation polymerization technique. The molecular weight of polyamides prepared from 1,4-phenylenediamine increases greatly with a reaction temperature above 260°C. The physical properties of the polyamides, such as glass transition temperature (T_g), melting point (T_m), decomposition temperature (T_d), crystalline behavior, and mechanical strength strongly depend on their molecular weight and flexibility of diamines used. The aromatic-based polyamides have a higher T_g, T_m, T_d, and stronger mechanical strength than that of aliphatic-based polyamides. X-ray diffraction patterns of the samples indicate that all of the resins synthesized present a typical semicrystalline morphology. Polyamides made from hydrogenated dimer acid possess lower T_g and higher mechanical strength, compared with polyamides from unsaturated dimer acid with different dimer and trimer ratios. These results are analyzed and discussed in accordance with the influence of rigid aromatic segments and the microstructure of different dimer acids. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:305–314, 1998     

Soluble wholly aromatic polyamides containing unsymmetrical pyridyl ether linkages

Wholly aromatic polyamides were synthesized from the amidation reaction between unsymmetrical diamine containing a pyridyl ether linkage and aromatic dicarboxylic acid chloride. The resulting polyamides containing pyridyl ether linkages showed high thermal stability (T_d5=467 °C) and enhanced solubility in organic solvents compared with the analogous polyamides having phenyl ether linkages. Substitution of just a single atom in a repeating unit was effective to disrupt the strong inter-chain interaction of parent aramid polymers.     

Aromatic polyamides. V. Substituent effect on thermal properties

Some wholly aromatic polyamides derived from unsubstituted and chloro- and nitro-substituted diamines have been studied from the viewpoint of their thermal stability, thermo-oxidative stability, and thermal transitions. General relationships between thermal stability of a polymer and its chemical structure are described. Decrease in thermal stability of poly(1,3-phenyleneisophthalamide) and poly(1,4-phenyleneterephthalamide) due to substituents has been explained and supported in part by infrared spectral data. The effect of electron-withdrawing substituents such as chloro and nitro in increasing the thermo-oxidative resistance of the polyamides is pointed out. The thermal transitions (T_g and T_m) of these polymers are also reported. All the polyamides exhibit a broad exothermic peak in the 630–700°C temperature range, which probably corresponds to reactions (crosslinking and cyclization) responsible for the high char yield of these systems.     

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     

Polyamides incorporating furan moieties: 4. Synthesis,characterisation and properties of a homologous series

Interfacial polycondensation of 2,2′‐bis[2‐(5‐chloroformylfuryl)]propane with various diamines gave high yields of a novel series of furanic polyamides with high inherent viscosities. The properties of these polymers (T_g, surface energy, crystallinity, thermal stability) were assessed and examined in terms of the role of the specific structure of the bridging group borne by the diamines. Only three polyamides were partially crystalline, whereas all the others were amorphous. Thermogravimetric analysis revealed that thermal decomposition began above 300 °C in all instances. © 2001 Society of Chemical Industry     

Influence of morphology on the properties of segmented block copolymers

A comparison was carried out regarding the structure and properties of segmented block copolymers with either non-crystallisable or crystallisable rigid segments. The flexible segment in the block copolymers was a linear poly(propylene oxide) end capped with poly(ethylene oxide), with a segment molecular weight of 2300 g/mol. The rigid segments were either non-crystallisable or monodisperse crystallisable polyamides of varying lengths. The morphologies were studied by TEM and AFM, the thermal mechanical properties by DMA and the elastic properties by compression set and tensile measurements. A direct comparison was made of segmented block copolymers with either liquid-liquid demixed or crystallised structures. The crystallised amide segments were more efficient in increasing the modulus and improving the elastic properties than the non-crystallisable ones. The copolymers with crystallised structures were transparent, had a low glass transition temperature of the polyether phase and a modulus that was independent of temperature between T_g and T_m. These copolymers also displayed a very low loss factor (tan δ), suggesting excellent dynamic properties. The hard phase in segmented block copolymers should thus preferably be crystalline.     

Inexpensive synthesis of 1,4-bis(4-aminophenoxy)-2- (6-oxido-6H-dibenz <c,e> <1,2> oxaphosphorin-6-yl) phenylene and its oxygen-plasma resistant polyamides

Inexpensive synthesis of diamine, 1,4-bis(4-nitrophenoxy)-2-(6-oxido-6H-dibenz <c,e> <1,2> oxaphosphorin-6-yl) phenylene was revealed in this work. Based on the diamine, a series of organosoluble polyamides were prepared by direct polycondensation of the diamine with various aromatic diacids using triphenyl phosphite and pyridine as condensing agents. The number-average molecular weights of the resulting polyamides range from 4.2 × 10⁴ to 10.5 × 10⁴ g/mol, and the weight-average molecular weights are in the range of 7.5-28.2 × 10⁴ g/mol. The T_gs of these polyamides range from 210 to 255 °C by dynamic mechanical analysis. The resulting polyamides are tough and flexible with tensile strength, elongation at break and moduli range from 84 to 101 MPa, 4.8-7.0%, and 2.36-3.22 GPa, respectively. The degradation temperatures (T_d 5%) and char yields at 800 °C in nitrogen range from 460 to 486 °C and 59-68 wt%, respectively. The cutoff wavelength of these polyamides falls in the range of 345-366 nm, showing a very light color characteristic. In addition, these polyamides display good oxygen plasma resistance.     

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.     

Composites of anionic (co)polyamides (nylon 6/nylon 12) with short glass E-fibers. Preparation and properties

The recent high demand of thermoplastic composites has induced an extensive experimentation and utilization of polyamides as thermoplastic sheet composites. The hand layup technique was used for the preparation of the glass fiber polyamide composites studied here. The percentage crystallinity of the composites was determined with a variety of techniques such as differential thermal analysis (DTA), wide-angle X-ray diffraction (WAXD) patterns, and density measurements. Glass transitions (T_g) and melting temperatures (T_m) were determined with DTA and dynamic mechanical thermal analyzer (DMTA) measurements. Finally, the mechanical properties (stress–strain curves and compression tests) were investigated and the results were correlated to the glass fiber content, and the percentage of the comonomer unit (caprolactam and laurolactam) in the polyamide composite. © 1994 John Wiley & Sons, Inc.     

Synthesis, characterisation and degradability of polyamides derived from aldaric acids and chain end functionalised polydimethylsiloxanes

Activated glucaric and galactaric acid derivatives were reacted with two different α,ω-diaminoalkyl polydimethylsiloxanes to give novel carbohydrate-segmented silicone polyamides, which were characterised by spectroscopic methods. Their intrinsic viscosities, Huggins constants, molecular weights and thermal properties have been determined by viscosimetric analysis, size exclusion chromatography, differential scanning calorimetry and thermal gravimetric analysis, respectively. Due to the immiscibility of carbohydrates and silicones, some of the presented materials demonstrate strong microphase separation with T_gs up to 144 °C. It could be shown, that galactaric acid segmented silicones display a higher T_g than their glucaric acid analogues. By varying the contents of glucaric and galactaric acid in a homologous series, which was dominated by cyclic products, as could be shown by MALDI TOF MS, the observed DSC signals could be shifted between 28 and 54 °C. In a first test on biodegradability, employing Proteinase XIV from Streptomyces griseus, it could be shown that this class of materials can be at least partly degraded by enzymes, with the amide bond functioning as a predetermined breaking point.     

Synthesis and study of some newer polyamides for semipermeable membrane

A series of novel polyamides was prepared by low temperature solution polycondensation of N-(p/m-aminobenzoyl aminoacetyl)-N'-(4/3-aminobenzoyl) hydrazine with different diacid chlorides in dry N,N-Dimethylacetamide (DMAC). The properties of the polyamides for membrane processing were studied with the help of infrared spectra, inherent viscosity, differential thermal, and thermogravimetric analysis. The inherent viscosities were measured in concentrated sulfuric acid at 25±5°C and were in the range of 0.35–0.89 dL/g. The thermogravimetric data in air indicate that the initial decomposition temperature was in the range of 175–200°C. The polymer melt temperature (T_m) and glass transition temperature (T_g) were in the range of 230–450°C and 153.3–300°C, respectively.     

Aging of poly(lactide)/poly(ethylene glycol) blends. Part 1. Poly(lactide) with low stereoregularity

Poly(lactide) (PLA) is rapidly gaining interest as a biodegradable thermoplastic for general usage in degradable disposables. To improve mechanical properties, a PLA with low stereoregularity was blended with polyethylene glycol (PEG). Blends with up to 30 wt% PEG were miscible at ambient temperature. Blending with PEG significantly decreased the T_g, decreased the modulus and increased the fracture strain of PLA. However, the PLA/PEG 70/30 blend became increasingly rigid over time at ambient conditions. The mechanism of aging primarily under ambient conditions of temperature and humidity was studied. Changes in mechanical properties, thermal transitions and solid state morphology were examined over time. Aging was caused by slow crystallization of PEG. Crystallization of PEG depleted the amorphous phase of PEG and gradually increased the T_g. As T_g approached the aging temperature, reduced molecular diffusivity slowed the crystallization rate dramatically. Aging essentially ceased when T_g of the amorphous phase reached the aging temperature. The increase in matrix T_g and the reinforcing effect of the crystals produced a change in mechanical properties from elastomer-like to thermoplastic-like.     

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.     

Synthesis of high performance polyamides utilizing copper‐catalyzed amidation of a dibromoarene with different diamides

A series of diphenylquinoxaline‐containing polyamides were prepared from the condensation polymerization of 2,3‐bis (4‐bromophenyl) quinoxaline (DBQ) with various primary and secondary diamides via copper‐catalyzed amidation reaction. The polyamides were characterized with FTIR, NMR, GPC, differential scanning calorimeter, and thermo gravimetric analysis, and their solubility and viscosity were measured. The polyamides synthesized here are amorphous and showed relatively good solubility in polar aprotic solvents and demonstrate the ability to form brownish hard films by solvent casting; their inherent viscosities ranged from 49 to 55 mL/g. The average molecular weights of polyamides were in the range of M_w = 11,950–5592 g/mol (MWD = 1.21–1.87). These polyamides had relatively high thermal stability with T_g values up to 276°C, 10% weight loss temperatures (T_10%) in the range of 364–476°C, and char yields at 600°C in N₂ up to 72%. They also exhibit emission in the solid state and in dilute (0.2 g/dL) DMAc solution at 425–484 nm with photoluminescence quantum (?_f) yields in the range of 14–23%. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Polyamides based on diamines containing aryloxy groups: Structure-property relationships

Aromatic polyamides containing different numbers of p-oxyphenylene groups and different catenated positions in the benzene rings were prepared from terephthalic acid (TPA) and isophthalic acid (IPA) with various aryloxy-containing diamines by means of the phosphorylation polycondensation reaction. Most of the polyamides were moderately to highly crystalline, as indicated by X-ray diffraction and DSC measurements. Polyisophthalamides were readily soluble in polar amide-type solvents such as N-methyl-2-pyrrolidone (NMP) and N,N-dimethylacetamide (DMAc). Some non-crystalline polyamides could afford tough films by solution casting. Most polyisophthalamides revealed discernible glass transition on their DSC curves, and their T_g values were recorded in the range of 215–238 °C. No discernible glass transitions were observed for the polyamides of TPA by DSC. The thermal stability of these polymers did not show clear dependence on the structure of the diacid or the diamine. In addition, a series of polyamides having pendant groups was synthesized from the polycondensation of TPA and IPA with 1,4-bis(4-aminophenoxy)benzene and its derivatives with methyl, tert-butyl, or phenyl substituent on the central benzene ring. In most cases, the incorporation of pendant groups generally resulted in an enhanced solubility and a decreased T_g and crystallinity.     

Effect of Piperazine Concentration on the Properties of Lower Purity Dimer Acid-Synthesized Polyamide Hot-Melt Adhesive

Abstract

Polyamide hot-melt adhesive was synthesized from lower purity, i.e., 75% purity dimer acid, sebacic acid, ethylenediamine and piperazine. The effect of piperazine content on the properties of polyamides, such as thermal properties: heat of fusion (H _f), heat of crystallization (H _c), softening point (T _s) and glass transition temperature (T _g); mechanical properties: tensile strength and hardness; adhesion properties: lap shear strength (LSS) and T-peel strength (TPS); and rheological properties was investigated. Concentration of piperazine was varied from 12.5 to 37.5 molar %. It was found that H _f, H _c, T _s, T _g, tensile strength, hardness, LSS, TPS and viscosity all increased with decrease in molar percentage of piperazine. This is due to increase in crystallinity of the polyamide with decrease in piperazine, giving better packing of molecules in the adhesive, thus giving better properties.     

Pulsed n.m.r. studies of molecular motion in wet nylon-6,6 fibres

The influence of water molecules on molecular motion in commercial nylon-6,6 fibres has been investigated by pulsed n.m.r. techniques. Transient n.m.r. signals, T₂ and T₁ relaxation times for the fibre protons were measured as a function of temperature and moisture (D₂O) content. Above the glass transition temperature, T_g, of the fibre, separation of the signal into two components, a ‘rigid’ and ‘non-rigid’ fraction, was possible. For wet fibres, the temperature at which the ‘non-rigid’ or ‘mobile’ component appeared was reduced as the water content was increased and the ‘mobile fraction’ increased with temperature. This behaviour is explained in terms of the mobilization of amorphous chain segments above the T_g and their ability to be ‘plasticized’ by water molecules. The effect of D₂O molecules and paramagnetic Mn²⁺ ions on T₁ relaxation of rigid and mobile segments provided further information on the properties of accessible chain segments between and on the crystallite surfaces. A chain folded model of semi-crystalline morphology has been adopted throughout the discussion.     

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.