Diacid Chlorides Research Articles

Synthesis and Investigation of Polyester and Poly Amide Azo Dyes (I)

The preparation of monomer dyes was carried out by formation of diazinium salt of amine compound to coupled with Ρ- toluidine, aniline to form azo dyes with function (hydroxy and amino) groups. the polymerized was carried out with different diacid chloride or modified with acroyl chloride to polymerize with methylmethacrylate (MMA) by two method solution and interfacial poly condensation methods, the prepared mono azodye, poly(ester) and poly(amide) azopolymers were characterized, by infrared spectroscopy, elemental analysis, 1H NMR, thermodynamic (TGA), thermo gravimetric (DSC) analysis and TGA. The molecular weights were measured by GPC. The synthesized polymers showed a good film forming properties.

Production of 5-(chloromethyl)furan-2-carbonyl chloride and furan-2,5-dicarbonyl chloride from biomass-derived 5-(chloromethyl)furfural (CMF)

Biomass-derived CMF is oxidized to the acid chloride CMFCC in a single step using inexpensivet-butyl hypochlorite. Likewise, DFF, also a CMF derivative, is oxidized directly to the diacid chloride FDCC. The products are platforms for a variety of chemical derivatives of carbohydrates.

Preparation and characterization of novel optically active poly(amide‐imide)/α‐Fe2O3 nanocomposites containing l‐alanine moieties

An optically active poly(amide‐imide) (PAI) was synthesized from the polymerization reaction of N,N′‐(Pyromellitoyl)‐bis‐l‐alanine diacid chloride with 2,5‐diaminotoluene. The obtained inorganic metal oxide nanocomposites composed of PAI/nanostructured hematite (α‐Fe2O3) were synthesized through ultrasonic irradiation. The resulting nanocomposites were characterized by Fourier transform infrared spectroscopy, powder X‐ray diffraction, transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). The TEM results indicated that the nanoparticles were dispersed homogeneously in PAI matrix on nanoscale. TGA confirmed that the heat stability of the nanocomposites was improved in the presence of α‐Fe2O3 nanoparticles. POLYM. COMPOS., 37:1805–1811, 2016. © 2014 Society of Plastics Engineers

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 5 a-5 f 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 LiCl 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 dL/g. On the other hand the corrosion inhibitive properties of monomer 3 as well as polyamides 5 d and 5 f 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 5 d 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 5 d and at 0.5 mg/L to reach 87.75% for polymer 5 f.

Blue light-emitting polyamide and poly(amide-imide)s containing 1,3,4-oxadiazole ring in the side chain

A new diamine monomer containing a 1,3,4-oxadiazole ring, 4,4′-diamino-4″-[2-(4-phenoxy)-5-(4-dimethylaminophenyl)-1,3,4-oxadiazole]triphenylmethane, was synthesized and characterized. The diamine is used to prepare novel polyamide and poly(amide-imide)s via a polycondensation reaction with various diacid chlorides in N-methyl-2-pyrrolidone. The structures of the monomers and polymers are characterized by means of FTIR, 1H, 13C and 15N NMR spectroscopy. The polymers result in high yields, and exhibit film forming ability and good solubility in many organic solvents. They show high thermal stability, with decomposition temperature being above 420 °C. The optical properties, absorption and fluorescence characteristics, in solution and solid state, are investigated. Solutions of the polymers exhibit fluorescence in the blue region, having high quantum yield in the range of 38.5–58.1%, and large Stokes shift values (110–120 nm). The introduction of hydrochloric acid into the polymer solutions has a significant effect upon the optical properties. Fluorescence quenching in the presence of 2,5-dinitrophenol was analysed using Stern–Volmer equation.

Preparation and characterization of new optically active poly(amide-imide)s and poly(ester-imide)s containing calix[4]arene units

This article describes the synthesis and characterization of new optically active polymers containing upper rim calix[4]arene from the polycondensation reaction of 5,11,17,23-tetra-tert-butyl-25,27-bis[(4-aminobenzyloxy)-6,28-dihydroxy] calix[4]arene with N,N′-pyromellitoylimido-bis-L-alanine diacid chloride (6a) and N,N′-pyromellitoylimido-bis-L-phenyl alanine diacid chloride (6b). This optically active diacidchlorides 6a and 6b have been prepared from the reaction of pyromellitic dianhydride with two chiral amino acids, alanine and phenyl alanine. The chiral poly(amide-imide)s and poly(ester-imide)s obtained in good yield and moderate inherent viscosity. All the polymers have been fully characterized by FTIR, 1H NMR spectroscopy and elemental analysis.

Novel species of soluble thermally stable poly(keto ether ether amide)s: preparation, characterization, and properties

A new diamine containing one keto and four ether groups was prepared through a three‐step reaction: first, hydroquinone was reacted with 1‐fluoro‐4‐nitrobenzene and 4‐(4‐nitrophenoxy) phenol was obtained. The next step was reduction of nitro group to amino group in which 4‐(4‐aminophenoxy) phenol was prepared. In the final step, the new diamine named as bis(4‐(4‐(4‐aminophenoxy)phenoxy)phenyl) methanone was synthesized through reaction of the later compound with 4,4′‐difluoro benzophenone. All prepared materials were fully characterized by spectroscopic methods and elemental analysis. Novel species of poly(keto ether ether amide)s were synthesized via polymerization reaction of the diamine with different diacid chlorides including terephthaloyl chloride, isophthaloyl chloride, and adipoyl chloride. All polyamides were characterized, and their properties such as thermal behavior, thermal stability, solubility, viscosity, water uptake, and crystallinity were investigated and compared together. The glass transition temperatures of the polymers were about 204–232°C, and their 10% weight losses were in the range of 396–448°C. Polymers showed high thermal stability and enhanced solubility that mainly resulted from incorporation of the diamine structure containing keto, ether, and aromatic units into polyamide backbones. Copyright © 2014 John Wiley & Sons, Ltd.

Organosoluble and optically active polyamides based on axially asymmetric 9,9′-spirobifluorene moieties

Optically active polyamides containing axially asymmetric 9,9′-spirobifluorene units in the main chain were synthesized for the first time by low-temperature solution polycondensation of ( R)-2,2′-bis(4-amino-2-trifluoromethylphenoxy)-9,9′-spirobifluorene with various diacyl chlorides. All these polymers were obtained in quantitative yields with inherent viscosities of 0.28–0.43 dL g−1. These polyamides were amorphous and readily soluble in many organic solvents such as N-methyl-2-pyrolidone, N, N-dimethylacetamide (DMAc), dimethyl sulfoxide, and tetrahydrofuran. The glass transition temperatures of these polyamides were recorded in the range of 199–261°C by differential scanning calorimetry, and the 10% weight loss temperatures were over 410°C both under nitrogen and in air atmospheres. The specific rotations of these chiral polyamides oscillated between 65.0° and 127.8° depending on the structures of the diacid chlorides. All the optically active polymers exhibited high chiral stability in solid state or in DMAc solvent at high temperature due to incorporation of chiral spirobifluorone unit in polymer backbones. The ultraviolet–visible and circular dichroism spectroscopic properties of these chiral polyamides in solutions were also studied.

Helium Recovery by Membrane Gas Separation Using Poly(o-acyloxyamide)s

Poly(o-acyloxyamide)s (PORAs) derived from a poly(o-hydroxyamide) from 2,2′-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (APAF) diamine, APAF–POHA, have been synthesized and evaluated as gas separation materials. PORAs were synthesized from poly(o-hydroxyamide)s by derivatization of the free OH group with an aliphatic acid dichloride or dianhydride that allowed the introduction of acetyl or pivaloyl groups on their structure. All of them showed low–medium thermal stability due to a degradation of the amide moieties, and most of them (those synthesized from isophthaloyl dichloride (IPC), 2,2′-bis(4-carboxyphenyl) hexafluoropropane dichloride (6FC), and 4,4′-dicarboxydiphenylsulfone dichloride (DPSC)) showed good mechanical properties. The poly(o-acyloxyamide)s synthesized have shown good permselectivities for He/N2 and He/CH4 separations and very good permeability–selectivity balance for He/CO2 separation. The acetyl PORAs showed better permeability versus selectivity balances than the pivaloyl ones. Moreover, selectivity increased while permeability decreased in the sequence 6F-APAF > IP-APAF > DPS-APAF. Intersegmental distances, d-spacing, were shown to decrease along this sequence, obtaining a nice correlation between permeability and d-spacing. For the He/N2 and the He/CH4 pairs of gases, the best permeability–selectivity values are obtained for 6F-APAF-Ac with a He permeability of 33 barrer and selectivities of 84 and 106, respectively. DPS-APAF-Ac gives a He permeability of 13 barrer and a selectivity of 21 for the He/CO2 separation.

Cyclodextrin polymers as highly effective adsorbents for removal and recovery of polychlorobiphenyl (PCB) contaminants in insulating oil.

A total of 179 countries (parties) ratified the Stockholm Convention on persistent organic pollutants (POPs) and agreed to destroy polychlorobiphenyls (PCBs) and develop a sound management plan by 2028. Currently, still 3 million tons of PCB-contaminated oil and equipment need to be managed under the Stockholm Convention. Thus, the development of a facile and environmentally benign method to treat large amounts of oil stockpiles contaminated with PCBs is a crucial subject. Herein, we report that cyclodextrin (CD) polymers, which are easily prepared by cross-linking the renewable cyclic oligosaccharide γ-cyclodextrin (γ-CD) with dibasic acid dichlorides, are a new selective and powerful adsorbent to remove PCB contaminants in oil. When PCB (100 ppm)-contaminated oil was passed through a column packed with the terephthaloyl-cross-linked γ-CD polymer (TP-γ-CD polymer) at 80-110 °C, the PCB contaminants were completely removed from the oil. Additionally, methyl esterification of the free carboxylic groups of the TP-γ-CD polymer enabled the complete recovery of the PCBs adsorbed on the polymer (with >99.9% recovery efficiency) by simply washing with acetone. The methyl-esterified TP-γ-CD polymer could be recycled at least 10 times for PCB adsorption without any loss in the adsorption capability. These results revealed that the γ-CD polymers can function as highly effective and powerful adsorbents for the removal and recovery of PCBs from PCB-contaminated oil and, thus, significantly contribute to the protection of the global environment.

Preparation of PET/clay nanocomposites via in situ polymerization in the presence of monomer‐activated organoclay

Various polyethylene terephthalate (PET)/clay nanocomposites containing a commercial organoclay (organophilic montmorillonite nanoclay [OMMT]) and a monomer‐activated OMMT (remodified OMMT) were prepared via in situ interlayer polycondensation of dimethyl terephthalate and ethylene glycol. In order to remodify the commercial OMMT nanoparticles, a diacid chloride monomer was applied. The prepared nanocomposites were characterized by diverse methods, including X‐ray diffraction, differential scanning calorimetry, thermogravimetric analysis, and intrinsic viscosity measurements. The results of the study revealed that the PET/(remodified OMMT) nanocomposites possess a better state of clay dispersion as well as significantly better thermal properties as compared with the PET/OMMT nanocomposites. Moreover, the PET/(remodified OMMT) nanocomposites showed higher crystallization temperature, degree of crystallinity, maximum degradation temperature, and lower half‐time of crystallization than that of the PET/OMMT nanocomposites. It was found that the remodification process for OMMT led to less of a foaming problem during in situ polymerization. J. VINYL ADDIT. TECHNOL., 21:70–78, 2015. © 2014 Society of Plastics Engineers

Synthesis of C2‐Symmetric Bisphosphine Ligands from Tartaric Acid, and Their Performance in the Pd‐Catalyzed Asymmetric O‐Allylation of a Phenol

AbstractStarting from tartaric acid derived chiral diols or dicarboxylic acid dichlorides with either a 2,2‐dimethyl‐1,3‐dioxolane (Taddol) or a 2,3‐dimethoxy‐2,3‐dimethyl‐1,4‐dioxane (Tatrol) core structure, and BH3‐protected ortho‐phosphanyl phenols, a set of fourteen new C2‐symmetric diphosphine ligands was synthesized. In addition, three related ligands were obtained from ortho‐diphenylphosphino‐anilines. The fully characterized ligands were then tested in the Pd‐catalyzed enantioselective O‐allylation of 4‐methoxyphenol using crotyl methyl carbonate as a reagent. In addition, a pseudo‐intramolecular variant of the reaction, using crotyl 4‐methoxyphenyl carbonate as a substrate, was studied. The so‐called Trost ligand was used as a reference. Although the Trost ligand (3 mol‐%) gave up to 84 % ee, one of the new ligands showed higher activity (50 % ee with 0.075 mol‐%).

Synthesis and characterization of novel aromatic poly(benzimidazole-amide)/Ag and Cu nanocomposites through transition metal complexation

A new thermally stable aromatic poly(benzimidazole-amide)s PBIAs was synthesized by low-temperature polycondensation of bis-benzimidazole diamines; 1,4-bis(5-amino-1H-benzimidazol-2-yl)benzene (3a) and 1,3-bis(5-amino-1H-benzimidazol-2-yl)benzene (3b) with two different diacid chlorides. Diamines 3a and 3b were prepared via direct condensation of 1,2-phenylene diamine and terephthalic or isophthalic acid in polyphosphoric acid in high yield. Chemical structures of synthesized monomers were confirmed by elemental analyses and spectroscopic methods. The structures of synthetized polymers were confirmed by FT-IR, 1H-NMR, elemental and thermogravimetric analysis (TGA), X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM). Thermal stability of the polymers was ascertained via 10 % weight loss temperatures in the range of 315–380 °C (inert atmosphere). Existence of benzimidazole moieties in polymer’s structure makes them suitable for easy coordination to Lewis acids or metallic ions, whereas the substitution of C–H or N–H protons allows for the synthesis of complex derivatives. As a result, a series of novel nanocomposites, via metal complexation of PBIA6a due to their great solubility with Ag+ or Cu2+ cations followed by reduction to metals by sodium borohydride (NaBH4), was prepared. The resulting nanocomposites’ structures were confirmed by FT-IR, XRD, TGA, UV/vis, FE-SEM, TEM and scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM–EDX). The FE-SEM, TEM and SEM–EDX results indicated that Cu and Ag particles were dispersed homogenously in nano scale in the polymer matrix.

Synthesis and processability into textile structures of radiopaque, biodegradable polyesters and poly(ester‐urethanes)

Radiopaque biodegradable polymers have been synthesized by ring‐opening polymerization of l/dl‐lactide and caprolactone with the iodine‐containing starter molecule 2,2‐bis(hydroxymethyl)propane‐1,3‐diyl bis(2,3,5‐triiodobenzoate) followed by chain elongation with a diacid chloride or diisocyanates. The resulting polyesters and poly(ester‐urethanes) exhibited a radiopacity of 60−124% relative to an aluminium sample of the same thickness. The polymers were processed into monofilament fibres by melt‐spinning and into fibre meshes by electrospinning. All polymers were biodegradable in simulated body fluid medium under in vitro conditions and showed an excellent in vitro cytocompatibility even after several months of hydrolytic degradation. A current drawback is the relatively low tensile strength of the polymer monofilaments, which needs to be improved for applications as textile structures. Nevertheless, the new radiopaque and biodegradable polymers are promising candidates in fields of application where radiopacity of implants is an important parameter.

Self-assembled aromatic polyamide nanofibers with trifluoromethyl groups via precipitation polymerization

Aromatic polyamide nanofibers with trifluoromethyl groups were prepared from a diacid chloride and a diamine in dioxane solution with a water content of 9vol%, via precipitation polymerization. The resulting nanofibers had an average diameter of approximately 50nm and were highly intertwined. The reaction solution exhibited high viscosity, resulting in the formation of a gel, due to strong interactions between the polymer and the solvent. It was determined that, during the fiber formation process, the product in the reaction solution transitioned from particles into fibers with a concurrent increase in molecular weight. As the reaction time was prolonged following the formation of the fibers, both the polymer's degree of crystallinity and the hydrogen bonding between polymer chains increased, while the morphology of the product became less regular.

Periodically Clickable Polyesters: Study of Intrachain Self-Segregation Induced Folding, Crystallization, and Mesophase Formation

A series of polyesters based on 2-propargyl-1,3-propanediol or 2,2-dipropargyl-1,3-propanediol or 2-allyl-2-propargyl-1,3-propanediol and 1,20-eicosanedioic acid were prepared by solution polycondensation using the corresponding diacid chloride; these polyesters were quantitatively "clicked" with a fluoroalkyl azide, namely CF3(CF2)7CH2CH2N3, to yield polyesters carrying long-chain alkylene segments in the backbone and either one or two perfluoroalkyl segments located at periodic intervals along the polymer chain. The immiscibility of the alkylene and fluoroalkyl segments causes the polymer chains to fold in a zigzag fashion to facilitate the segregation of these segments; the folded chains further organize in the solid state to form a lamellar structure with alternating domains of alkyl (HC) and fluoroalkyl (FC) segments. Evidence for the self-segregation is provided by DSC, SAXS, WAXS, and TEM studies; in two of the samples, the DSC thermograms showed two distinct endotherms associated with the melting of the individual domains, while the WAXS patterns confirm the existence of two separate peaks corresponding to the interchain distances within the crystalline lattices of the HC and FC domains. SAXS data, on the other hand, reveal the formation of an extended lamellar morphology with an interlamellar spacing that matches reasonably well with those estimated from TEM studies. Interestingly, a smectic-type liquid crystalline phase is observed at temperatures between the two melting transitions. These systems present a unique opportunity to develop interesting nanostructured polymeric materials with precise control over both the domain size and morphology; importantly, the domain sizes are far smaller than those typically observed in traditional block copolymers.

Synthesis and Characterization of New Polyamides Containing Thianthrene Moiety and Based on Dibenzylidene Derivatives

A new series of polyamides based on diarylidene derivatives were synthesized from 2,5bis(m-aminobenzylidene)cyclopentanone VIII, 2,6-bis(maminobenzylidene)cyclohexanone IX, 2,7-bis(m-aminobenzylidene) cyclheptanone X and bis(m-aminobenzylidene) acetone XI by reaction with diacid chlorides of thianthrene (2,7Dichloroformylthianthrene -5,5`,10,10`-tetraoxide IV. using solution polycondensation technique. These polymers ranged from yellow to orange color and had inherent viscosity up to 1.08-0.65 dL/g. All the polyamides were insoluble in common organic solvents but dissolved completely in concentrated H2SO4. The thermal stabilities of the prepared polyamides were evaluated by TGA and DSC analyses. The morphological properties of some selected polyamides were detected by SEM.

Scalable synthesis and derivation of functional polyesters bearing ene and epoxide side chains

Functional polyester chemistry is well suited to improve delivery of biomacromolecular drugs because it enables tuning of degradation profiles and inclusion of key functional groups (e.g. cationic charges for nucleic acid binding). However, current approaches to introduce functionality suffer from inadequate scalability and modularity. We have developed a scalable library of functional polyesters based on the polymerization of trimethylolpropane allyl ether (TPAE) with diacid chlorides (poly(TPAE-co-AC)s). The reactive side chains can be easily modified with various functional thiols (e.g. alkyl-, amino-, and PEG-) and amines to generate a diverse set of materials, thereby tuning the chemistry for potential opportunities in drug delivery. The polymerization occurs readily under mild conditions at room temperature with Mw for poly(TPAE-co-suberoyl chloride) exceeding 42000 g mol−1. In addition, poly(TPAE-co-adipoyl chloride) was polymerized on a 100+ gram scale in 71% final isolated yield. Due to the structural similarity to established non-functional polyesters such as PLGA, these new materials may find broad application as functional polyesters for gene delivery, tissue engineering, and other nanotechnology applications.

Synthesis of New Aza Thia Crowns Bearing 2,2′-Diaminodiphenyl Disulfide

New aza thia crowns were prepared from the reaction of 2,2′-diaminodiphenyl disulfide and diacids or diacid chlorides. Diacids are malonic acid, adipic acid, sebacic acid, and 2,2′-thiodiacetic acid and diacid dichlorides are malonyl chloride, adipoyl chloride, sebacoyl chloride, and 2,2′-thiodiacetyl chloride. [Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional figures.]

Annulations of α‐Carbamoyl Ketene Dithioacetals with Dicarboxylic Acid Dichlorides: Synthesis of Functionalized Pyrrolidinetriones and Piperidinetriones

AbstractAn annulation strategy based on ketene dithioacetals is described. Under very mild conditions, a number of pyrrolidinetriones 2 and piperidinetriones 3 have been synthesized by the cycloaddition reaction of α‐carbamoyl ketene dithioacetals 1 with di‐carboxylic acid dichlorides in good to excellent yields. Further application of this protocol is highlighted by the synthesis of a set of fused pyrimidine derivatives 4/5 from 2/3 and amidines.