Synthesis and thermal properties of soluble silicon containing phenylated aromatic–aliphatic polyamides

Journal of Thermal Analysis and Calorimetry - Aromatic polyamides find many applications in diverse and critical areas due to their high thermal stability coupled with high mechanical properties....     

Synthesis and properties of polyamides from 2,5-furandicarboxylic acid and aromatic and aliphatic diamines

Russian Chemical Bulletin - Polyamides based on the 5-hydroxymethylfurfural derivative (2,5-furandicarboxylic acid dichloroanhydride) and diamines of both aromatic and aliphatic series were...     

Dynamic mechanical properties of aromatic,aliphatic, and partially fluorinated epoxy resins

The α, β, and γ transitions at temperatures between ?200 and +100°C. of crosslinked aromatic and aliphatic epoxy polymers were determined from damping and shear modulus data, and compared with their fluorine containing analogs. Loci of segmental relaxation are suggested at various temperatures, and similarities between aliphatic and fluorocarbon segments, and polyethylene and polytetrafluoroethylene are discussed. Two systems of structurally similar monomers 2,2,3,3,4,4-hexafluoropentane diglycidyl ether-1,5 and 1,4-butane diglycidyl ether, and 2,2-bis(4-glycidyl phenyl ether)hexafluoropropane and 2,2-bis(4-glycidyl phenyl ether) propane were polymerized with the aid of two diamine curing agents, namely, ethylenediamine and m-xylylenediamine. Polymers of the aromatic diepoxides showed transitions with peaks at ?56°C. and above +70°C. Three main peaks were registered for the aliphatic and fluorocarbon diepoxides: at ?125 and at ?100°C., at ?56°C., and at 0°C. It is suggested that the T_g is affected by an interdependence of relaxation of all components of the polymer main chain.     

Preparation and properties of polyamides from 4-phenoxy- and 4-phenylthio-m-phenylenediamine and both aromatic and aliphatic diacids

New soluble aramids having pendant phenoxy and phenylthio groups were prepared in high molecular weights by the polycondensation of aromatic diacids with 4-phenoxy-m-phenylenediamine and 4-phenylthio-m-phenylenediamine, respectively. Glass transition temperatures (T_g) of these aramids were in the range 195–255°C, where T_gs of phenoxy pendant aramids were higher than those of phenylthio substituted aramids. These properties were compared with those of the parent aramids derived from m-phenylenediamine and aromatic diacids. Aromatic-aliphatic polyamides were also prepared by the reaction of these three diamines with aliphatic diacids having 4–10 methylene groups and were characterized in detail.     

Thermal properties of wholly aromatic polyamides

Various wholly aromatic polyamides based on m-and p-phenylene diamines and isophthaloyl and terephthaloyl chloride have been synthesized and their thermal properties and oxygen index values have been studied. The effect of different substituents on the aromatic ring of the diamine have been explored by comparing their differential thermal analysis (DTA) and thermogravimetric analysis (TGA) behavior, their relative char yields at 700°C, and their oxygen indices. The ? Cl, ? NO₂, and ? OH substituted polyamides have been found to produce the highest char yields. The high char yields are probably associated with crosslinking occurring at high temperatures. Attempts at correlating char yield with oxygen index indicated enhancement for the chlorosubstituted aramids.     

Lower-frequency infrared spectra and structures of some typical aliphatic polyamides

The Polarized lower-frequency infrared spectra (800–33 cm^-1) of nylon 66 (α form), nylon 77 (γ form), and nylon 6 (both α and γ form) have been examined. The spectral changes which occur on complex formation of the polyamides with iodine-potassium iodide solution and on subsequent iodine desorption have been studied in relation to the changes in the polymer structures. On the basis of these results, most of the stronger bands have been reasonably assigned to the vibrations characteristic of the amide group and the methylene chain of the polyamides, and some new structure–frequency correlations have been established for the polymers.     

Synthesis and characterization of some novel organometallic aromatic polyamides

Some novel ferrocene containing aromatic polyamides were prepared by low‐temperature solution phase polycondensation of 1,1′‐ferrocenedicarboxylic acid chloride with some newly synthesized aromatic diamines in tetrahydrofuran, in the presence of triethylamine. The amorphous polymers were derived in good yields, and did not melt at >350 °C. The monomers and the resulting polymers were characterized by their physical properties, elemental analysis, ¹H‐NMR, FTIR spectroscopy, differential scanning calorimetry and thermogravimetric analyses. The polymeric products were insoluble in common solvents tested. However, all were miscible in concentrated H₂SO₄, forming reddish brown solutions at ambient conditions. The glass transition temperatures (T_g) of these polymers were quite high, which is characteristic of aramids. They are stable up to 500 °C, with 10% mass loss observed in the range 400–650 °C. The activation energies of pyrolysis for each of the products were calculated by Horowitz and Metzger's method. Solution viscosities of the polymers were reduced in concentrated sulfuric acid, which is due to their non‐Newtonian behavior. Copyright © 2006 John Wiley & Sons, Ltd.     

Mass spectra of some partially fluorinated aliphatic compounds

The mass spectra of several fluorohydrocarbons are shown and discussed. The fragmentation of these compounds displays a close correlation with the molecular structure and points to the importance of the charge-stabilisation concept for the ion intensities. The iodo-derivatives show a large abundant molecular ion.     

Calculated polarizabilities for some aliphatic and aromatic hydrocarbons

Ground-state molecular polarizabilities of some aliphatic and aromatic hydrocarbons have been calculated using the method of Marchese and Jaffé. The polarizability components for the typical normal alkane n-heptane are found to be very nearly independent of conformation; those for biphenyl show a significant dependence but the average polarizability is approximately constant. The polarizabilities of the n-alkanes in general are seriously underestimated, but relatively good agreement with experiment is obtained for benzene and biphenyl.     

Synthesis and characterization of some aromatic polyamides containing double bonds

Ten polyfumaramides based on fumaric acid and aromatic diamines and six polystilbenediamides based on 4,4′-stilbenedicarboxylic acid and aromatic diamines were synthesized and characterized by solubility, viscosity, density, infrared and UV-visible spectroscopy, and thermal analyses. Variation in properties with structure is discussed here.     

Aromatic polyamides. II. Thermal degradation of some aromatic polyamides and their model diamides

Thermal degradation behavior of poly(1,3-phenylene isophthalamide) and poly(chloro-2,4-phenylene isophthalamide) was investigated with the aid of some appropriate model compounds. The pyrolysis products of these materials were identified by gas chromatography (GC), gas chromatography/Fourier transform infrared spectroscopy (GC/FT-IR), and gas chromatography/mass spectrometry (GC/MS). The residual chars were characterized by IR spectroscopy. Thermogravimetric analysis (TGA) was applied to study the effect of end-group concentration on the degradation characteristics of the two polyamides. Kinetic parameters that describe the thermal degradation of the polyamides were also evaluated by TGA. The results of this investigation suggest that the thermal decomposition of these aromatic polyamides involves homolytic as well as hydrolytic cleavages of the amide units.     

Synthesis and liquid crystal properties of bipyridine-containing aromatic polyamides

A series of novel aromatic polyamides containing 2,2′-bipyridine moiety were synthesized by polycondensation of 2,2′-bipyridine-5,5′-dicarboxylic acid ( 2 ) with various aromatic diamines in hexamethylphosphoramide (HMPA) containing lithium chloride. The resulting polyamide solutions in 98% sulfuric acid and in HMPA-LiCl exhibited lyotropic liquid crystal phases. The phase transition behaviors were studied by polarizing microscopy and X-ray diffraction. The polyamides also formed metal complexes with cis-dichlorobis(bipyridine)ruthenium dihydrate [cis-Ru(bpy)₂Cl₂ · 2H₂O] which was supported by changes in electronic spectra.     

Aromatic polyamides. I. Synthesis and characterization of some aromatic polyamides and their model diamides

The synthesis of some wholly aromatic polyamides based on unsubstituted and chloro- and nitro-substituted diamines by low temperature solution polymerization is described. Poly(1,3-phenylene isophthalamide) and poly(chloro-2,4-phenylene isophthalamide) were selected for further investigation. To study the two polyamides on a systematic basis their model diamides were synthesized. These materials were characterized with respect to chemical structure and purity by elemental analysis, infrared (IR), and nuclear magnetic resonance (NMR) spectroscopic techniques. The usefulness of the model compounds in the interpretation of the polymer spectra is also demonstrated.     

Preparation and properties of fluorine-containing aromatic polyamides from tetrafluorophthaloyl chlorides and aromatic diamines

New fluorine-containing aromatic polyamides with inherent viscosities of 0.4–1.8 dL/g were prepared by the low temperature solution polycondensation of tetrafluoroisophthaloyl and tetrafluoroterephthaloyl chlorides with N,N′-bis(trimethylsilyl)-substituted aromatic diamines. The aromatic polyperfluoroisophthalamides were amorphous polymers with glass transition temperatures around 280°C, whereas the polyperfluoroterephthalamides were crystalline. Most of these aromatic polyamides were soluble in organic solvents, and began to decompose around 330°C in air or nitrogen atmosphere.     

Preparation and properties of aromatic polyamides and copolyamides from phenylindanedicarboxylic acid and aromatic diamines

Aromatic polyamides (aramids) having inherent viscosities of 0.5–1.10 dL/g were prepared by the direct polycondensation of 1,1,3-trimethyl-3-(4-carboxyphenyl)indane-5-carboxylic acid with various aromatic diamines using triphenyl phosphite and pyridine as the condensing agents. Copolyamides were also prepared by a similar procedure from a mixture of the phenylindane diacid, terephthalic acid, and p-phenylenediamine. Almost all of the aramids were soluble in a variety of solvents such as N-methyl-2-pyrrolidone, pyridine, and m-cresol, and afforded transparent and tough films by the solution casting. These aramids and copolyamides had glass transition temperatures in the range of 290–355°C, and started to lose weight at 340°C in air.     

Synthesis and properties of aromatic polyamides containing the cyclohexane structure

1,1-Bis[4-(4-carboxyphenoxy)phenyl]cyclohexane (III) and 1,1-bis[4-(4-aminophenoxy)phenyl]cyclohexane (V) were prepared in two main steps starting from the aromatic nucleophilic substitution of p-fluorobenzonitrile and p-chloronitrobenzene, respectively, with 1,1-bis(4-hydroxyphenyl)cyclohexane in the presence of potassium carbonate in N,N-dimethylformamide (DMF). Using triphenyl phosphite and pyridine as condensing agents, two series of polyamides with cyclohexylidene cardo groups were directly polycondensated from dicarboxylic acid III with various aromatic diamines or from diamine V with various aromatic dicarboxylic acids in an N-methyl-2-pyrrolidone (NMP) solution containing dissolved calcium chloride. The polyamides exhibited inherent viscosities in the range of 0.45 to 1.78 dL/g. Almost all of the polymers were readily soluble in polar aprotic solvents such as NMP and N,N-dimethylacetamide (DMAc) and could afford transparent, flexible, and tough films by solution casting. The glass transition temperatures (T_g) of these aromatic polyamides were in the range of 180–243°C by DSC, and the 10% weight loss temperatures in nitrogen and air were all above 450°C. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3575–3583, 1999     

Preparation and properties of aromatic polyamides from 5-t-butylisophthalic acid and various aromatic diamines

Aromatic polyamides (aramids) having pendant t-butyl group were synthesized by the direct polycondensation of 5-t-butylisophthalic acid with various aromatic diamines in N-methyl-2-pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. The aramids having inherent viscosities of 0.6–2.4 dL/g were obtained in quantitative yields. These polymers were readily soluble in various solvents such as NMP,N,N-dimethylacetamide, dimethyl sulfoxide, and pyridine, and gave transparent, tough and flexible films by casting from the NMP solutions. The aramids had glass transition temperatures between 250 and 330°C, and started to lose weight around 350°C, with 10% weight loss being recorded at about 450°C in air.     

Alternating melting points,heats and entropies of fusion of linear aliphatic polyesters

Heats of fusion of polyethylene-adipate, pimelate, suberate and azelaate have been determined by two methods, viz. DTA and the pressure dependence of the melting point up to 6000 bar. Degrees of crystallization were measured dilatometrically. Entropies of fusion were divided into volume and conformational entropy terms, only the latter alternates. Alternation of melting points depends on enthalpy of fusion ΔH_m, entropy of fusion ΔS_m and volume change Δυ on melting; influence of the functions increases thus ΔV_m < ΔH_m < ΔS_m and ΔS_m is dominant. Entropy and heat of fusion alternation is explained by the conformational change on melting governed by the driving force of maximum H-bridge formation.     

Chemical ionization mass spectrometry of some aromatic and aliphatic oximes

Aromatic and aliphatic oximes are protonated under methane or isobutane chemical ionization conditions. The structural identity of the [MH? H₂O]⁺˙ ions with nitrilium cations is established by the mass analysed ion kinetic energy method after collisional activation. The results also show the stereospecific nature of the transposition in the gas phase.