Poly(amideimide)s containing pendant pentadecyl chains: Synthesis and characterization

A new aromatic diacylhydrazide monomer viz., 4-[4′-(hydrazinocarbonyl)phenoxy]-2- pentadecylbenzohydrazide was synthesized starting from cardanol, which in turn is obtainable from cashew nut shell liquid - a renewable resource material. A series of new poly(amideimide)s containing flexibilizing ether linkages and pendant pentadecyl chains was synthesized from 4-[4′-(hydrazinocarbonyl)phenoxy]-2-pentadecylbenzohydrazide and commercially available aromatic dianhydrides, viz., benzene-1,2,4,5-tetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, benzophenone-3,3′,4,4′-tetracarboxylic dianhydride, 4,4′-oxydiphthalic anhydride and 4,4′-(hexafluoro isopropylidene)diphthalic anhydride by a two-step solution polycondensation in N,N-dimethylacetamide via the poly(hydrazide acid) intermediate. Inherent viscosities of poly(amideimide)s were in the range 0.60-0.64 dL/g in N,N-dimethylacetamide at 30 ± 0.1 °C. Poly(amideimide)s could be solution cast into tough, transparent and flexible films from their N,N-dimethylacetamide solutions. The solubility of poly(amideimide)s was significantly improved by incorporation of pendant pentadecyl chains and were found to be soluble in N,N-dimethylacetamide, 1-methyl-2-pyrrolidinone, pyridine and m-cresol at room temperature or upon heating. Wide angle X-ray diffraction patterns of poly(amideimide)s revealed a broad halo at around 2θ = ∼19° suggesting that polymers were amorphous in nature. In the small-angle region, diffuse to sharp reflections of a typically layered structure resulting from the packing of pentadecyl side chains were observed. The temperature at 10% weight loss (T₁₀), determined by TGA in nitrogen atmosphere, of poly(amideimide)s was in the range of 388-410 °C indicating their good thermal stability. Glass transition temperatures of poly(amideimide)s were in the range 162-198 °C. It was observed that the plasticization effect of attached pentadecyl side chains induced the depression of T_g.     

Synthesis and characterization of aromatic polyazomethines bearing pendant pentadecyl chains

Aromatic diamine monomer viz., 4-(4′-aminophenoxy)-2-pentadecylbenzenamine containing pendant pentadecyl chain was synthesized starting from cashew nut shell liquid - a renewable resource material and was characterized by FTIR, ¹H and ¹³C NMR spectroscopy. A series of new (co) polyazomethines containing pendant pentadecyl chains and flexibilizing ether linkages was synthesized by polycondensation of 4-(4′-aminophenoxy)-2-pentadecyl benzenamine with commercially available aromatic dialdehydes viz., terephthaldehyde (TPA), isophthaldehyde (IPA) and varying mixture of TPA and IPA. Inherent viscosities and number average molecular weights of (co) polyazomethines were in the range 0.50-0.70 dL/g and 10,490-40-800 (GPC, polystyrene standard), respectively indicating formation of medium to reasonably high molecular weight polymers. (Co) polyazomethines containing pendant pentadecyl chains were found to be soluble in common organic solvents such as chloroform, dichloromethane, tetrahydrofuran, pyridine, m-cresol and could be cast into transparent and stretchable films from their solution in chloroform. (Co) polyazomethines were essentially amorphous in nature and the formation of loosely-developed layered structure was observed arising from the packing of pendant pentadecyl chains. Polyazomethines exhibited glass transition temperatures (T_g) in the range 21-48 °C. The observed depression of glass transition temperature could be ascribed to the “internal plasticization” effect of pentadecyl chains. The temperature at 10% wt loss (T₁₀), determined from TGA in nitrogen atmosphere of polyazomethines were in the range 434-441 °C indicating their good thermal stability.     

Synthesis and characterization of new polyimides containing pendent pentadecyl chains

A new unsymmetrical aromatic diamine, viz., 4-pentadecylbenzene-1,3-diamine was synthesized through a series of reaction steps starting from 3-pentadecylphenol. 4-Pentadecylbenzene-1,3-diamine was employed to synthesize a series of new polyimides by one-step polycondensation in m-cresol with four commercially available aromatic dianhydrides, viz., 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA), 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), 4,4′-oxydiphthalic anhydride (ODPA) and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6-FDA). Inherent viscosities of resulting polyimides were in the range 0.33-0.67 dL/g and number average molecular weights were in the range 14,700-52,200 (GPC, polystyrene standard). Polyimides containing pendent pentadecyl chains were soluble in organic solvents such as chloroform, m-cresol, N,N-dimethylacetamide (DMAc), 1-methyl-2-pyrrolidinone (NMP), pyridine and nitrobenzene. Strong and flexible films of polyimides could be cast from their chloroform solutions. Polyimides exhibited glass transition temperature in the range 158-206 °C. The temperature at 10% wt. loss (T₁₀), determined by TGA in nitrogen atmosphere, of polyimides was in the range 470-480 °C indicating good thermal stability.     

Soluble aromatic polyamides modified by incorporation of 1,2,4-triazole and pentadecyl units into the backbone of polymer

Abstract

A new series of soluble aromatic polyamides was synthesized by low temperature solution polycondensation of novel aromatic diamine namely 3,5-bis-(4′-amino phenyl)-4-(4″-methoxy-2″-pentadecyl phenyl) 1,2,4-triazole (VII) with aromatic diacid chlorides, viz. isophthaloyl chloride (IPC) and terephthaloyl chloride (TPC). The aromaticdiamine (VII) was characterized by elemental analysis, FT-IR, NMR (¹H, ¹³C), and mass spectrometry. Copolyamides were also synthesized by employing various mole proportions of IPC and TPC with diamine (VII). Inherent viscosities of these polyamides were in the range of 0.50–0.65 dL/g in DMAc, indicating formation of moderate to high molecular weight of polyamides. These polyamides showed good solubility in polar aprotic solvents such as N,N-Dimethyl acetamide (DMAc), N-Methyl 2-pyrrolidone (NMP), N, N, Dimethyl formamide (DMF), and Dimethyl sulphoxide (DMSO), which may be due to incorporation of pendant methoxyphenyl moiety with pentadecyl units. The amorphous morphology of polyamides as evidenced by XRD. These polyamides had lower glass transition temperatures; as determined by DSC, compared to the T_g of conventional aromatic polyamides due to internal plasticization effect of long alkyl pentadecyl group. Polymers showed good thermal stability, with initial decomposition temperature above 300?°C.     

Synthesis and characterization of Schiff-base-containing polyamides

A series of new Schiff base polyamides（PAs） were synthesized by polycondensation of benzilbisthiosemicarbazone diamine（LH₆） with different commercially available aliphatic and aromatic diacid chlorides. The monomer and all the PAs were characterized by FTIR,¹H-NMR,and elemental analysis.The prepared polyamides showed inherent viscosities in the range of 0.30-0.36 dL/g in DMF at 25℃,indicating their moderate molecular weight.The PAs were completely soluble in aprotic polar solvents such as dimethylformamide（DMF）,N-methylpyrolidone（NMP）, tetrachloroethane（TCE）,dimthylsulfoxide（DMSO） and also in H₂SO₄ and partially soluble in THF,acetone and chloroform at room temperature.Thermal analysis showed that these PAs were practically amorphous and exhibited 10%weight loss above 220℃.     

Synthesis and characterization of processable polyamides containing polar quinoxaline unit in the main chain and evaluation of its hydrophilicity

Here we report a new five polyamides prepared via solution-phase polycondensation under Yamazaki-Higashi conditions to prove the suitability of this method. The synthesized polyamides were characterized by FTIR, ¹H-NMR, differential scanning calorimetry, thermogravimetric analysis, inherent viscosity, solubility and wettability tests. These polyamides were amorphous in nature and they are completely soluble in many organic solvents and they could easily be solution-cast into transparent, flexible films. The as-prepaired polymers showed excellent thermal properties. The glass transition temperatures of these polymers are in the range of 251–274?°C under nitrogen atmosphere. The decomposition temperature in nitrogen for a 10% weight-loss temperature is more than 744?°C, and char yield at 900?°C ranged from 43 to 56% in nitrogen. Water contact angles were also tested to know the hydrophilicity of the polyamide films. As-synthesized polyamides showed smallest quantact angles indicating hydrophilic surface.     

Synthesis,characterization and corrosion inhibitive properties of new thiazole based polyamides containing diarylidenecyclohexanone moiety

The present work aimed to synthesize a new interesting series of thiazole based polyamides containing diarylidenecyclohexanone moiety 5a-5f using low temperature solution polycondensation technique. The new polymers were synthesized by the reaction of thiazole based monomer namely, bis(2-aminothiazol-4-ylbenzylidene)cyclohexanone 3 with different aliphatic and aromatic diacid chlorides using NMP, and in the presence of anhydrous Li Cl as catalyst. Adipoyl, sebacoyl, oxaloyl, terephthaloyl, isophthaloyl dichlorides and biphenyl dicarbonyl dichloride were used as diacid chlorides. The structure of the model compound 4 as well as the new polymers was confirmed by correct elemental and spectral analyses. The thermal properties of those polymers were evaluated by TGA and DTG measurements and correlated to their structural units, beside X-ray diffraction analysis, solubility and viscometry measurements. The inherent viscosities for the synthesized polymers were in the range 0.6–1.03 d L/g. On the other hand the corrosion inhibitive properties of monomer 3 as well as polyamides 5d and 5f as selected examples were carried out on carbon-steel in 0.5 mol/L H2SO4 at 40 °C. The calculated inhibition efficiency(IE%) for polymer 5d was in the range(82 ± 6)% in all selected concentrations. The best value of IE% was obtained at 1 mg/L to reach 98.24% for polymer 5d and at 0.5 mg/L to reach 87.75% for polymer 5f.     

Synthesis and characterization of organosoluble polyamides from quinoxaline based diamine

<正>Aromatic/aliphatic polyamides were synthesized from a diamine monomer,2,3-bis-p-aminophenylquinoxaline (Ⅳ),based on quinoxaline and various dicarboxylic acids of aliphatic,aromatic and heterocyclic.The diamine and polyamides were characterized by elemental analysis,FTIR and ~1H-NMR.The solubility of the polyamides was affected by the quinoxaline and heterocyclic groups in the polymer chain.They were all soluble in common organic solvents such as dimethylsulfoxide(DMSO),N,N-dimethylformamide(DMF) and N-methylpyrolidone(NMP).The polyamides showed inherent viscosity in the range of 0.25-0.3 dL/g in DMSO at 25℃and good thermal stability with the char yields in the range of 65%-82%at 600℃in nitrogen.     

Regularly alternating poly(amideimide)s containing pendent pentadecyl chains: Synthesis and characterization

Two new aromatic diamines containing preformed amide linkages, viz., N,N′-(4-pentadecyl-1,3-phenylene)bis(4-aminobenzamide) I and N,N′-(4-pentadecyl-1,3-phenylene)bis(3-aminobenzamide) II, were synthesized by reaction of 4-pentadecylbenzene-1,3-diamine with 4-nitrobenzoylchloride and 3-nitrobenzoylchloride, followed by reduction of the respective dinitro derivatives. A series of new poly(amideimide)s was synthesized by polycondensation of I and II with four commercially available aromatic dianhydrides, viz., pyromellitic dianhydride (PMDA), 4,4′-biphenyltetracarboxylic dianhydride (BPDA), 4,4′-oxydiphthalic anhydride (ODPA), and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6-FDA) in N,N-dimethylacetamide (DMAc) employing conventional two step method via poly(amic acid) intermediate followed by thermal imidization. Reference poly(amideimide)s were synthesized by polycondensation of N,N′-(1,3-phenylene)bis(4-aminobenzamide) and N,N′-(1,3-phenylene)bis(3-aminobenzamide) with the same aromatic dianhydrides. Inherent viscosities of poly(amideimide)s containing pendent pentadecyl chains were in the range 0.37-1.23 dL/g in N,N-dimethylacetamide at 30 ± 0.1 °C indicating the formation of medium to high molecular weight polymers. The poly(amideimide)s containing pendent pentadecyl chains were found to be soluble in N,N-dimethylacetamide, N,N-dimethylformamide, 1-methyl-2-pyrrolidinone and pyridine and could be cast into transparent, flexible and tough films from their N,N-dimethylacetamide solution. Wide angle X-ray diffraction patterns exhibited broad halo indicating that the polymers were essentially amorphous in nature. X-ray diffractograms also displayed sharp reflection in the small angle region (2θ ≈ 3°) for poly(amideimide)s containing pentadecyl chains indicating the formation of layered structure arising from packing of flexible pentadecyl chains. The glass transition temperatures observed for reference poly(amideimide)s were in the range 331-275 °C and those for poly(amideimide)s containing pendent pentadecyl chains were in the range 185-286 °C indicating a large drop in T_g owing to the “internal plasticization” effect of pentadecyl chains. The temperature at 10% weight loss (T₁₀), determined by TGA in nitrogen atmosphere, were in the range 460-480 °C indicating their good thermal stability.     

Synthesis and characterization of novel aromatic polyamides derived from two heterocyclic diamines

Two diamines were synthesized as new aromatic monomers. A series of novel aromatic polyamides (aramids) were also synthesized by direct and indirect polycondensation of these diamines with various aromatic dicarboxylic acids. These aramids have inherent viscosities of 0.43-0.84 dl/g and were obtained in quantitative yield.     

Synthesis and characterization of aromatic polymers containing pendant silyl groups. II. Aromatic polyamides

In order to improve the solubility of aromatic polyamides without significant loss of thermal stability, synthesis of aromatic polyamides containing pendant silyl groups was carried out by direct polycondensation of silylated aromatic diacids such as 2-trimethylsilylterephthalic acid (TSTA), 2,5-bis (trimethylsilyl) terephthalic acid (BTSTA), 5-trimethylsilylisophthalic acid (TSIA), 5-dimethylphenylsilylisophthalic acid (DMSIA), and 5-triphenylsilylisophthalic acid (TPSIA) with various aromatic diamines. The resulting polyamides had inherent viscosities in the range of 0.18–1.10 dL/g and showed improved solubilities toward aprotic polar solvents such as NMP, DMF, DMSO, etc. The prepared aromatic polyamides exhibited fairly good thermal stabilities, which were almost comparable to those of corresponding nonsubstituted aromatic polyamides. That is, thermogravimetric analysis (TGA) data revealed 10% weight losses at 358–500°C and residual weights at 700°C were 46–67% under nitrogen atmosphere. © 1992 John Wiley & Sons, Inc.     

Synthesis and characterization of a novel two-dimensional layered vanadate complex containing double helical chains

A novel two-dimensional layered vanadate complex 1 [Ni(phen)H₂O][V₂O₆] has been hydrothermally synthesized and characterized by elemental analyses, i.r., x.p.s., t.g. and single crystal X-ray diffraction. The single crystal X-ray diffraction analysis reveals that compound 1 consists of the chains covalently linked by [Ni(phen)H₂O]²⁺ subunits to form two-dimensional layered polyoxovanadate. It is interesting that the compound 1 consists of left-handed and right-handed helical chains, which are further interconnected to produce the double helical chains. The adjacent two-dimensional layers interact with each other via extensive hydrogen bonds and π–π stacking interactions to form a three-dimensional supramolecular framework.     

Dual-responsive shape memory and self-healing ability of a novel copolymer from epoxy/cashew nut shell liquid and polycaprolactone

In this work, the blends of epoxy (EP) and polycaprolactone (PCL) with a bio-based curing agent, viz. cashew nut shell liquid (CNSL) were studied for their dual-responsive shape memory and self-healing behaviors. The suitable EP/CNSL weight ratio was observed at 70/30. The increase of PCL content up to 20 wt% in EP-CNSL matrix significantly enhanced the shape memory response to both thermal and chemical stimuli. All specimens showed 100% thermo-responsive shape recovery and the recovery time decreased with increasing PCL content. In the case of chemo-responsive shape memory, the immersion times spent for 100% shape recovery in water and methanol substantially decreased when PCL was added. Moreover, after thermal treatment, the EP-CNSL matrix with 20 wt% PCL showed significant self-healing ability with high tensile strength recovery at 93.70%. The EP-CNSL/PCL copolymer could be a promising alternative bio-related smart material for various applications such as dual-activated sensors and coatings with self-healing ability.     

Synthesis and characterization of novel ferroelectric liquid crystal polysiloxane containing undecanoyloxy spacer (I)

A novel side-chain liquid crystal polysiloxane and its corresponding monomer were synthesized by the standard method. We ensured their structures were as expected and their purities were high by ¹H nuclear magnetic resonance and infrared measurements. They were studied by differential scanning calorimetry (DSC) for their thermal analysis and polarizing optical microscopy (POM) with hot stage for their textures and transition temperatures. The results showed good liquid crystal properties and low transition temperatures of the mesophase. X-ray diffractions were done to research their layer structure and SmA and SmC^* phases were assured, in good agreement with the results of the POM and DSC measurements. The optical rotation degree was also measured.     

Synthesis and characterization of poly(amideimide)s containing pendent flexible alkoxy chains

A series of aromatic diacylhydrazides containing pendent flexible alkoxy chains, viz., 5-butyloxyisophthalicacid dihydrazide, 5-octyloxyisophthalicacid dihydrazide, 5-dodecyloxyisophthalicacid dihydrazide and 5-hexadecyloxyisophthalicacid dihydrazide were synthesized by the hydrazinolysis reaction of the corresponding aromatic esters with hydrazine hydrate. Diacylhydrazides were each polycondensed with aromatic dianhydrides, viz., 4,4′-oxydiphthalic anhydride (ODPA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA) to obtain new poly(amideimide)s. Poly(amideimide)s had inherent viscosity in the range 0.55-0.88 dL/g in N,N-dimethylacetamide (DMAc) at 30 ± 0.1 °C. Poly(amideimide)s were found to be soluble in DMAc, N,N-dimethylformamide (DMF), 1-methyl-2-pyrrolidinone (NMP) and pyridine and could be cast into tough, flexible and transparent films from a solution in DMAc. X-ray diffractograms revealed that poly(amideimide)s with longer alkoxy chains had layered structures. Glass transition temperature of poly(amideimide)s containing pendent flexible alkoxy chains were in the range 215-245 °C. Temperature at 10% weight loss was in the range 380-410 °C in nitrogen atmosphere indicating good thermal stability of poly(amideimide)s.     

Synthesis and characterization of polyamides containing heterocyclic thiaxanthone units

Novel polyamides containing heterocyclic thiaxanthone units were prepared by condensing 2,7-dichloroformylthiaxanthone-5,5′-dioxide and 2,8-dichloroformylthiaxanthone-5,5′-dioxide with various aromatic diamines, under low temperature solution polymerization conditions in DMAc. The model diamide, 2,8-ditolylcarbamylthiaxanthone-5,5′-dioxide was synthesised and characterized by spectroscopic methods. The polyamides were prepared in 70–80% yield and had inherent viscosity in the 0.36–0.73 dL/g range. The poyamides have decomposition temperatures in the 425–510°C range in nitrogen. The effect of thiaxanthone rings on polymer backbone on solubility, crystallinity, and thermal stability is also discussed.     

Processable heat resistant polyamides containing tetraphenyl thiophene having pendant phenyl moiety with heterocyclic quinoxaline unit: Synthesis and characterization

A series of new polyamides containing tetraphenyl thiophene having pendant phenyl moiety with heterocyclic quinoxaline unit were synthesized by using the solution polycondensation method of novel diamine monomer V with isopthaloyl chloride (IPC) and terpthaloyl chloride (TPC) in various mole proportions. These novel polymers were characterized by FT-IR, solubility, inherent viscosity, thermal analysis and X-ray diffraction studies. Inherent viscosities of these polymers were in the range 0.66 to 1.44 dL/g indicating moderate to high molecular weight built-up. These polymers exhibited solubility in various solvents such as DMAc, NMP, pyridine, m-cresol etc. X-ray diffraction pattern of polymers showed that introduction of pendant phenyl moiety would disturb the chain regularity and packing, leading to amorphous nature. Thermal analysis by TGA and DSC showed excellent thermal stability of polymers. The structure -property correlation among these polyamides were studied, in view of these polymer's potential applications as processable high temperature resistance materials.     

Synthesis and characterization of aromatic polyamides containing alkylphthalimido pendent groups

A series of polyisophthalamides containing pendent phthalimido groups and flexible side spacers were prepared from four novel diacids and three commercial aromatic diamines. These polyamides were prepared in high yields and with high molecular weights by direct polycondensation with triphenyl phosphite and pyridine as condensing agents. The weight‐average and number‐average molecular weights, measured by gel permeation chromatography, were 70,000–137,000 and 47,000–86,000 g/mol, respectively. The novel polyamides were amorphous and readily soluble and showed glass‐transition temperatures of 150–240 °C, as measured by differential scanning calorimetry. Thermogravimetric analysis showed that the 10% weight‐loss temperatures in nitrogen were 355–430 °C, a significant improvement in thermal stability having been observed with the increase in the side‐chain length. A theoretical quantum mechanical study was successfully carried out to explain these results. Flexible and tough films, cast from polymer solutions, showed tensile strengths of 50–125 MPa. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3711–3724, 2002     

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.     

Synthesis and characterization of novel aromatic polyamides containing 3-trifluoromethyl-substituted triphenylamine

A new 3-trifluoromethyl-substituted triphenylamine-containing aromatic diacid monomer, N,N-bis(4-carboxyphenyl)-3-trifluoromethylaniline, was prepared by the substitution reaction of 3-trifluoromethylaniline with 4-fluorobenzonitrile, followed by alkaline hydrolysis of the dinitrile intermediate. Novel aromatic polyamides with 3-trifluoromethyl-substituted triphenylamine moieties were prepared from the diacid and various aromatic diamines via the direct phosphorylation polycondensation. All the polyamides were amorphous and readily soluble in many polar organic solvents such as N,N-dimethylacetamide and N-methyl-2-pyrrolidone, and could be solution-cast into transparent, tough, and flexible films with good mechanical properties. They exhibited good thermal stability with relatively high glass-transition temperatures (258–327°C), 10% weight-loss temperatures above 500°C, and char yields higher than 60% at 800°C in nitrogen. These polymers had low dielectric constants of 3.22–3.70 (100 Hz), low moisture absorption in the range of 1.75–2.58%, and high transparency with an ultraviolet–visible absorption cut-off wavelength in the 375–395 nm range. Cyclic voltammograms of the polyamide films cast onto an indium tin oxide coated glass substrate exhibited a reversible oxidation redox couple with oxidation half-wave potentials (E_1/2) of 0.95–1.00 V vs. Ag/AgCl in an acetonitrile solution.