Miscibility and Mechanical Properties of Poly(4,4′-diaminobenzanilide- 2,6-naphthalamide)/Nylon 6 Molecular Composites

Poly(4,4′-diaminobenzanilide-2,6-naphthalamide) (DBNA) was synthe-sized by reaction of 2,6-naphthalene dicarboxylic acid with 4,4′-diamino-benzanilide. A new family of molecular composites based on the synthesized DBNA and nylon 6 has been discovered. Exploratory studies were con-ducted with polymers that are soluble in a common organic solvent, N-methylpyrrolidone containing lithium chloride, so that a blend could be prepared by precipitating blended materials in solution into a non-solvent such as water. The miscibility of blends of DBNA with nylon 6 was studied using a differential scanning calorimeter, dynamic mechanical analyser and Fourier transform infrared spectrometer. The blends were found to have at least partial miscibility between DBNA and nylon 6. The morphology and mechanical properties of the molecular composites were evaluated using a scanning electron microscope, transmission electron microscope and tensile tester. The etched specimen showed microfibrils with a diameter of a few nanometres. It has been found that improvement in DBNA dispersion and mechanical properties can be obtained by blending small amounts of DBNA in nylon 6. © of SCI.     

Synthesis and characterization of novel wholly para‐oriented aromatic polyamide‐hydrazides containing sulfone‐ether linkages

Four novel wholly para‐oriented aromatic polyamide‐hydrazides containing flexibilizing sulfone‐ether linkages in their main chains have been synthesized from 4‐amino‐3‐hydroxy benzhydrazide (4A3HBH) with either 4,4′‐sulfonyldibenzoyl chloride (SDBC), 4,4′‐[sulfonylbis(1,4‐phenylene)dioxy]dibenzoyl chloride (SODBC), 4,4′‐[sulfonylbis(2,6‐dimethyl‐1,4‐phenylene)dioxy]dibenzoyl chloride (4MeSODBC), or 4,4′‐(1,4‐phenylenedioxy)dibenzoyl chloride (ODBC) via a low‐temperature solution polycondensation reaction. A polyamide‐hydrazide without the flexibilizing linkages is also investigated for comparison. It was synthesized from 4A3HBH and terephthaloyl chloride (TCl) by the same synthetic route. The intrinsic viscosities of the polymer ranged from 2.85 to 4.83 dL g^?1 in N,N‐dimethyl acetamide (DMAc) at 30°C and decreased with introducing the flexibilizing linkages into the polymer. All the polymers were soluble in DMAc, N,N‐dimethyl formamide (DMF), and N‐methyl‐2‐pyrrolidone (NMP), and their solutions could be cast into films with good mechanical strengths. Further, they exhibited a great affinity to water sorption. Their solubility and hydrophilicity increased remarkably by introducing the flexibilizing linkages. The polymers could be thermally cyclodehydrated into the corresponding poly(1,3,4‐oxadiazolyl‐benzoxazoles) approximately in the region of 295–470°C either in nitrogen or in air atmospheres. The flexibilizing linkages improve the solubility of the resulting poly(1,3,4‐oxadiazolyl‐benzoxazoles) when compared with poly(1,3,4‐oxadiazolyl‐benzoxazoles) free from these linkages. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Miscibility and mechanical properties of aryl-aliphatic polyamides/nylon 6 molecular composites

Summary A series of aryl-aliphatic polyamides, copoly(4,4-diaminobenzanilide-adipamide/2,6-naphthalamide)s, with feed mole ratios of adipic acid/2,6-naphthalene dicarboxylic acid of 1/9, 3/7, and 5/5 were synthesized. A new family of molecular composites based on the synthesized aryl-aliphatic polyamides and nylon 6 has been discovered. The molecular composites were found to have at least partial miscibility between aryl-aliphatic polyamides and nylon 6. Well-defined aryl-aliphatic polyamide microfibrils a few nanometers in diameter were observed in the molecular composites. 10 wt% aryl-aliphatic polyamide clearly promoted the toughness of nylon 6.     

Studies on a diphenylether modified poly(phenyl-1,4, phenylene terephthalate) liquid crystalline polymer and its blends with polycarbonate and polysulfone

Blends of a thermotropic liquid crystalline polymer, LCP, (4,4′-dicarboxy diphenyl ether modified poly(phenyl-1,4-phenylene terephthalate)) with polycarbonate and polysulfone were prepared and characterized with respect to their thermal properties, viscoelastic behavior, processability and mechanical properties. The processability of the thermoplastics was significantly improved by the addition of small amounts of LCP. This was also reflected by decreases in the steady shear viscosities, though the dynamic complex viscosities of the blends were generally similar or higher than those of the individual component polymers. Composite fibers were spun from the blends and the tensile moduli and strengths were consistent with a morphology of highly oriented LCP microfibrils with high aspect ratios dispersed in the thermoplastic fiber. The properties increased with increasing draw ratio.     

Synthesis and characterization of novel polyurethanes based on 4,4′-[1,4-phenylenedi-diazene-2,1-diyl]bis(2-carboxyphenol) and 4,4′-[1,4-phenylenedi-diazene-2,1-diyl]bis(2-chlorophenol) hard segments

Eight novel polyurethanes (PUs) based on 4,4′-[1,4-phenylenedi-diazene-2,1-diyl]bis(2-carboxyphenol) and 4,4′-[1,4-phenylenedi-diazene-2,1-diyl]bis(2-chloro- phenol) as hard segments with four diisocyanates viz., 4,4′-diphenyl-methane diisocyanate, toluene 2,4-diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate were prepared. Structural and thermal characterization of the segmented PUs were determined by FT-IR, UV spectrophotometry, fluoroscence spectroscopy, ¹H NMR, ¹³C NMR spectroscopy and DTA/TGA analysis. All the PUs contain domains of semi-crystalline and amorphous structures, as indicated by X-ray diffraction. PUs were soluble in polar aprotic solvents like N-methyl-2-pyrrolidone (NMP), dimethyl formamide (DMF) and dimethylsulfoxide (DMSO).     

Synthesis and characterization of polyimides and polyamide-imides containing azomethine linkages

Polyimides and polyamide-imides containing azomethine linkages in the polymer backbone have been synthesized from 4,4′-bis(4-isocyanatobenzylidene)-diaminodiphenylether (ODAI), 4,4′-bis(4-isocyanatobenzylidene)-diaminodiphenyl-methane (MADI), 4,4′-bis(4-isocyanatobenzylidene)-diaminodiphenylsulphone (SDAI), pyromellitic dianhydride (PMDA), 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA), and trimellitic anhydride (TMA), by a one-step process. The diisocyanates ODAI, MDAI and SDAI were prepared from the corresponding diacids, namely, 4,4′-bis(4-carboxybenzylidene)-diaminodiphenylether (ODAA), 4,4′-bis(4-carboxybenzylidene)-diaminodiphenylmethane (MDAA) and 4,4′-bis-(4-carboxybenzylidene)-diaminodiphenylsulphone (SDAA) by a Weinstock-modified Curtius rearrangement method. All the polycondensation reactions were conducted in N-methyl-2-pyrrolidone (NMP) under identical conditions and the polymers obtained were characterized by IR spectroscopy, solution viscosity, elemental analysis, thermogravimetric analysis, differential scanning calorimetry and X-ray diffraction.     

Synthesis and characterization of photoelectronic polymers containing triphenylamine moiety

Several polymers containing triphenylene moieties in main chain were synthesized by Knovenagel or Wittig condensations. The polymers were characterized by ¹H NMR, IR, GPC, TG, UV–vis, FL and CV. Results indicated that PNB, which was prepared from the polycondensation of 4,4′-dialdehyde-4″-n-butyltriphenylamine with 1,4-bis(triphenylphosphonionmethyl)benzene dibromide, is the most thermally stable one and that PNP, which was prepared from the polycondensation of 4,4′-dialdehyde-4″-n-butyltriphenylamine with p-phenylene diacetonitrile, is the most thermally instable one. The fluorescence quantum efficiency of PNB is 94.3%, which is a high value for optoelectronic polymer materials. All the polymers have a similar CV curve with a reversible oxidation peak and two reduction peaks except that PNB has a single reduction peak.     

Preparation and Properties of Cyano-Containing Polyimide Films Based on 2,6-Bis(4-aminophenoxy)- benzonitrile

Summary A series of cyano-containing polyimides were synthesized from 2,6-bis(4-amino- phenoxy)benzonitrile and some aromatic dianhydride monomers by solution polycondensation. The poly(amic acid) films could be obtained by solution-cast from N-methyl-2-pyrrolidinone solutions and thermally converted into tough polyimide films. Structure and physical properties of thin films of those polyimides were measured by FTIR, TGA, dynamic mechanical analysis and LCR hitester et al. Results showed that the polyimides prepared from 2,6-bis(4-aminophenoxy)- benzonitrile and 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride or 4,4’-(hexafluoropropylidene)diphthalic anhydride exhibited more excellent energy-damping characteristic and excellent solubility in NMP, DMF, DMAc, DMSO, THF and CHCl₃, whereas the polyimides from 2,6-bis(4-aminophenoxy)benzonitrile and 3,3’,4,4’-biphenyltetracarboxylic dianhydride or Pyromellitic dianhydride were insoluble in polar and nonpolar organic solvents. All polyimides indicated higher glass transition temperatures, excellent thermal stability and tensile properties. Incorporating a nitrile group into the polyimide backbone would enhance the dielectric constant of the polyimide films.     

Synthesis and characterization of novel benzhydrol-containing poly(amide-imide)s

A series of novel benzhydrol-containing poly(amide-imide)s (PAIs) have been prepared from a new diimide-dicarboxylic acid, N,N′-bis(4-hydroxycarbonyl)-benzhydrol-3,3′,4,4′-tetracarboxydiimide (BHTDA-DIA), with various diamines by direct polycondensation using triphenyl phosphite and pyridine as condensing agents. The polymers obtained had inherent viscosities of 0.35–0.96 dl g⁻¹. All these PAIs, except polymer PAI-2, were soluble in N-methyl-2-pyrrolidinone and N,N-dimethylacetamide containing LiCl (1 wt%). Tough and flexible PAI films could be obtained by casting PAIs from their DMAc or NMP solutions, except for polymer PAI-2. The polymer films had a tensile strength of 93–111 MPa, an elongation at break range of 4–6%, and an initial modulus range of 2.7–3.8 GPa. The glass transition temperatures of most polymers were found to be above 255 °C. These polymers were fairly stable up to a temperature around or above 400 °C, and lost 10% weight in the range 426–507 °C in nitrogen and 423–515 °C in air. © 1999 Society of Chemical Industry     

1,4-Bis(2,3-dicarboxyl-phenoxy)benzene dianhydride-based phenylethynyl terminated thermoset oligoimides for resin transfer molding applications

A series of thermoset oligoimides have been prepared by the thermal polycondensation of 1,4-bis(2,3-dicarboxyl-phenoxy)benzene dianhydride with three different aromatic diamines in the presence of 4-phenylethynylphthalic anhydride as an end capping reagent. The aromatic diamines included 4,4′-oxydianiline, 2,2′-bis(trifluoromethyl)benzidine (TFDB) and 2-phenyl-4,4′-diaminodiphenyl ether (p-ODA). Effects of the chemical structures and molecular weights of the oligoimides on their aggregated structures, melt processability as well as the thermal and mechanical properties of the cured films were then systematically investigated. X-ray diffraction results indicated that ODA series oligoimides and TFDB series oligoimides showed crystallinity; however, the asymmetrical p-ODA enables the p-ODA series oligoimides to exhibit amorphous forms. So the p-ODA based oligoimides with molecular weight of 750 g mol⁻¹ showed much lower melt viscosity at a low temperature and the melt viscosity could maintain below 1 Pa s⁻¹ after isothermal aging for 2 h at any temperature in the range of 220–280 °C by rheological measurements. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47967.     

Synthesis,characterization, and mechanical properties of an injection moldable polyimide based on 1,4-diaminobutane

A partially aliphatic polyimide was synthesized in a two-step process in N-methylpyrrolidone (NMP) from 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) and 1,4-diaminobutane (DAB). Weight average molecular weights ranging from 35,000 to over 160,000 were obtained by adding different amounts of the chain stopper phthalic anhydride, or by using a slight excess of BTDA. Rheological measurements, supported by a size exclusion chromatography (SEC) analysis before and after injection molding, point to branching or even partial crosslinking during molding of poly(BTDA-DAB) if reactive amine endgroups are present. By reacting these amine endgroups with benzoyl chloride, branching is limited and a more Newtonian flow is observed. Both non-endcapped and endcapped reactor powders are ∼60% crystalline (Tg = 170 to 175°C, Tm = 290 to 300°C), but according to wide and small angle X-ray scattering (WAXS and SAXS) studies on test bars, both the more linear polyimides and their branched counterparts are fully amorphous after injection molding. Nevertheless, poly(BTDA-DAB) shows interesting mechanical properties like a bending modulus of ∼3.9 GPa, a tensile strength of ∼130 MPa, a tensile elongation at break of ∼13%, and a notched Izod impact of ∼4 kJ/m².     

Synthesis and memory characteristics of polyimides containing noncoplanar aryl pendant groups

A series of soluble aromatic polyimides were prepared from 2,2′-diphenyl-4,4′-biphenyl diamine (DPBD), 2,2′-bis(biphenyl)-4,4′-biphenyl diamine (BBPBD), 2,2′-bis[4-(naphthalen-1-yl)phenyl]-4,4′-biphenyl diamine (BNPBD) and 2,2′-bis(3,5-dimethoxyphenyl)-4,4′-biphenyl diamine (BMPBD) by polycondensation with 2,2′-bis[4′-(3′′,4′′,5′′-trifluorophenyl)phenyl]-4,4′,5,5′-biphenyl tetracarboxylic dianhydride via a two-step procedure. The resulting polymers were fully characterized and they exhibited excellent organosolubility, high thermal and dimensional stability. Resistive switching devices with the configuration of Al/polymer/ITO were constructed from these polyimides by using conventional solution coating process. Devices with the active layer based on DPBD, BBPBD and BNPBD exhibited nonvolatile and rewritable flash type memory characteristics with the turn-on voltage at ?2.0 to ?3.0 V and the turn-off voltage at 2.0–3.0 V. Whereas, device based on BMPBD demonstrated a bipolar write-once read-many times (WORM) memory capability with the writing voltage around ±3.0 V. The ON/OFF current ratio of these devices was of about 10⁶ and the retention times can be as long as 10⁴ s.     

Interpenetrating polymer networks derived from epoxide-amine adducts in either polymer network

A new type of interpenetrating polymer network was synthesized via photoinitiated free-radical polymerization of α,ω-methacryloyl terminated macromonomers prepared from epoxide-amine-adducts, followed by thermal addition polymerization of bisphenol-A diglycidyl ether and 4,4′-diaminodiphenylsulfone or 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0.^2,6]decane. The interpenetrating polymer networks are optically transparent and show only one glass transition temperature ranging from -10 to 130°C, as a function of the macromonomer/addition polymer mixing ratio. The presence of a single phase was confirmed by scanning electron microscopy (SEM).     

Thermal and mechanical properties of thermoplastic polyurethane elastomers from different polymerization methods

Thermoplastic polyurethane elastomers (TPUs) based on 4,4′-methylene-diphenyl diisocyanate, poly(tetramethylene glycol), diamine-terminated aliphatic nylon oligomer, and 1,4-butanediol were synthesized by two different polymerization methods, i.e. one shot and prepolymer methods. The effects of the polymerization method on the thermal and mechanical properties of the TPUs have been studied. A broader distribution of hard segment lengths in TPUs prepared by the one shot method was observed from thermal and tensile property measurements, compared with those prepared by the prepolymer method. TPUs by the one shot method showed a higher T_m of the hard segments and better tensile properties when soft-hard segment interaction was relatively small. However, inferior tensile properties were observed when the soft-hard segment interaction was high; typically when nylon oligomer was used as a soft segment.     

Poly(pyridinium salt)s with organic counterions derived from an aromatic diamine containing oxyethylene unit exhibiting amphotropic liquid-crystalline and photoluminescence properties

Several poly(pyridinium salt)s containing various organic counterions and oxyethylene unit in their backbones were synthesized by either the ring-transmutation polymerization reaction of 4,4′-(1,4-phenylene)bis(2,6-diphenylpyrylium tosylate) with 1,2-bis(4-aminophenoxy)ethane on heating in dimethyl sulfoxide or the metathesis reaction of the tosylate polymer with the corresponding lithium or sodium salts in acetonitrile. Their chemical structures were determined by ¹H and ¹³C NMR spectroscopy, and elemental analyses. Their number-average molecular weights and polydispersity indices were in the range of 59,000-63,000 and 1.41-1.65, respectively, as determined by gel permeation chromatography. They were characterized for their thermotropic and lyotropic liquid-crystalline properties by using differential scanning calorimetry and polarizing optical microscopy. Since these polymers exhibited liquid-crystalline phase both in the melt and in solutions, they belong to an amphotropic class of ionic polymers. Their light-emitting properties both in polar organic solvents and in films cast from methanol and acetonitrile were also studied by using spectrofluorometry.     

Synthesis and properties of polyimides derived from diamine monomer containing bi-benzimidazole unit

A new aromatic heterocyclic diamine monomer containing bi-benzimidazole unit, 2,2-bis(4′-aminophenyl)-5,5-bi-1H-benzimidazole, was synthesized from 2,2-bis(4′-nitrophenyl)-5,5-bi-1H-benzimidazole (BNPBBI) prepared via the reaction of 3,3′,4,4′-biphenyltetramine and p-nitrobenzaldehyde with a high yield. Their compositions and chemical structures containing polybenzimidazole backbone were characterized by FTIR, ¹H NMR and elemental analysis. A series of aromatic polyimides containing the heterocyclic moiety in the main chain were prepared by the reaction of BAPBBI with various aromatic dianhydrides of 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic anhydride or pyromellitic dianhydride. The polymers possess a high glass transition temperature of >415 °C and a good thermal stability up to 566 °C with a 5 % weight loss. The combination of polybenzimidazole and polyimide via introducing BAPBBI into the main chains provides the rigid structure, and macromolecular interactions are thus enhanced, resulting in the outstanding mechanical properties. These polyimides exhibit the strong tensile strength of 201 to 327 MPa, and the ultrahigh tensile moduli of 10.7 to 15.5 GPa without post stretching.     

Aromatic polyamides bearing ether and isopropylidene or hexafluoroisopropylidene links in the main chain

Two multiring, flexible dicarboxylic acids, 4,4'-[isopropylidenebis(1,4-phenylene)dioxy] dibenzoic acid (3) and 4,4'-[hexafluoroisopropylidenebis(1,4-phenylene)dioxyldibenzoic acid (3-F), were synthesized through the nucleophilic fluorodisplacement ofp-fluorobenzonitrile by the dipotassium bisphenolates of the corresponding bisphenol precursors followed by alkaline hydrolysis. Two series of aromatic polyamides 5_a–k and 5_a–k-F containing both ether and isopropylidene or hexafluoroisopropylidene linkages between phenylene units were prepared by direct polycondensation of diacids 3 and 3-F, respectively, with various aromatic diamines using triphenyl phosphite and pyridine as condensing agents in aN-methyl-2-pyrrolidone (NMP) solution containing dissolved calcium chloride. The resulting polyamides of 5 and 5-F series have inherent viscosities of 0.92–1.29 dL/g and 0.60–0.92 dL/g, respectively. Most of these polymers are amorphous in nature, are soluble in polar solvents such as NMP,N,N-dimethylacetamide (DMAc), andN,N dimethylformamide (DMF), and can afford tough and flexible films by solution casting. Differential scanning calorimetry shows T_gs ranging from 175 to 239 °C for the 5 series polyamides and ranging from 172 to 267 °C for the 5-F series polymers. Both classes of polyamides show good thermal stability, with the 5-F series polyamides being more stable.     

Synthesis and characterization of highly soluble poly(ether imide)s containing indane moieties in the main chain

A new indane containing unsymmetrical diamine monomer ( 3 ) was synthesized. This diamine monomer leads to a number of novel semifluorinated poly (ether imide)s when reacted with different commercially available dianhydrides like benzene‐1,2,4,5‐tetracarboxylic dianhydride (PMDA), benzophenone‐3,3′, 4,4′‐tetracarboxylic dianhydride (BTDA), 4,4′‐(hexafluoro‐isopropylidene)diphthalic anhydride (6FDA), 4,4′‐oxydiphthalic anhydride (ODPA), and 4,4′‐(4,4′‐Isopropylidenediphenoxy)bis(phthalic anhydride) (BPADA) by thermal imidization route. All the poly(ether imide)s showed excellent solubility in several organic solvents such as N‐methylpyrrolidone (NMP), N,N‐dimethylformamide (DMF), N,N‐dimethylacetamide (DMAc), tetrahydrofuran (THF), chloroform (CHCl₃) and dichloromethane (DCM) at room temperature. These light yellow poly (ether imide)s showed very low water absorption (0.19–0.30%) and very good optical transparency. Wide angle X‐ray diffraction measurements revealed that these polymers were amorphous in nature. The polymers exhibited high thermal stability up to 526°C in nitrogen with 5% weight loss, and high glass transition temperature up to 265°C. The polymers exhibited high tensile strength up to 85 MPa, modulus up to 2.5 GPa and elongation at break up to 38%, depending on the exact polymer structure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of transparent polyetherketone

Transparent polymer with excellent heat resistance and mechanical properties play an important role in many fields. However, transparent polyetheretherketones films are rarely reported, probably due to their high crystallinity. In this work, a transparent polymer polyetherketone was prepared from the reaction of 4,4′-difluorobenzophenone, 2,6-bis(4-hydroxybenzylidene) cyclohexanone, and tert-butylhydroquinone in the presence of K₂CO₃. This new polymer has excellent thermal stability, high glass transition temperature (T_g = 172°C), good film-casting property, high transparency, good hydrophobicity, and low saturated water absorption (0.52%). The material has broad application prospects in flexible solar cells, UV protection, and thin insulation materials.     

Synthesis and characterization of a series of poly(alkylene carbonate) macrodiols and the effect of their structure on the properties of polyurethanes

A series of polycarbonate and copolycarbonate macrodiols was prepared by using an ester interchange reaction with ethylene carbonate and diols such as 1,6-hexanediol, 1,10-decanediol, 2,2-diethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, and 1,3-bis(4-hydroxybutyl)-1,1,3,3-tetramethyldisiloxane. The diols were chosen to prepare a series of macrodiols with different structural features including linear, branched, rigid, and flexible. The macrodiols were characterized by ¹H- and ¹³C-NMR spectroscopy and DSC. The commercial macrodiol based on 1,6-hexanediol exhibited a high level of crystallinity, while with the exception of 1,10-decanediol–based copolycarbonates all the others were completely amorphous. 1,10-Decanediol–based materials showed partial crystallinity under subambient conditions. A series of polyurethane elastomers with a constant hard segment percentage (40 wt %) was prepared using 4,4′-methylenediphenyl diisocyanate and 1,4-butanediol as the hard segment. Tensile test results and Shore hardness measurements demonstrated that polyurethanes based on polycarbonate macrodiols prepared from 1,3-bis(4-hydroxybutyl)-1,1,3,3-tetramethyldisiloxane had the lowest modulus and hardness of the series of polyurethanes. The remaining polyurethanes had high tensile strength with poor elasticity. The morphology of the polyurethanes, as determined by DSC analysis, varied from completely phase-mixed to well phase-separated structures. Polyurethanes based on macrodiols prepared from 1,3-bis(4-hydroxybutyl)-1,1,3,3-tetramethyldisiloxane showed good phase-separated morphology, with sharp hard segment melting endotherms and soft segment glass transitions close to that of the pure soft segment. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1621–1633, 1998