Aliphatic Diacid Chlorides Research Articles

Thermotropic Liquid Crystalline Polyesters Using Aromatic Rigid Diols, Unsaturated Fumaric Acid and Flexible Sebacic Acid

In the present study, seven different series of thermotropic liquid crystalline polyesters (TLCPs) containing unsaturated fumaroyl chloride and flexible sebacoyl chloride were synthesized using the interfacial polymerization methodology. Homopolyesters prepared with saturated flexible spacer such as sebacoyl chloride were mesomorphic whereas homopolyesters synthesized using unsaturated aliphatic spacer such as fumaroyl chloride that was non-mesomorphic. Aromatic diad and triad based mesogenic diols were selected as rigid moiety for liquid crystalline phase formation. Within each series, copolyesters were synthesized by varying relative mole ratio of the above two aliphatic diacid chlorides. Most of the liquid crystalline polyesters showed solubility in phenol:tetrachloroethane (60:40) at 40 ᵒC.

Conformational and Structural Changes with Increasing Methylene Segment Length in Aromatic–Aliphatic Polyamides

The synthesis and structural characterization of various aromatic–aliphatic polyamides are reported in this study. The polymers are obtained by solution polymerization of p-phenylenediamine with various aliphatic diacid chlorides. The resulting polyamides are labeled PA P-X, where X varies between 5 and 10 and corresponds to the number of carbon atoms of the dicarboxylic acid monomers used in the synthesis. The polyamides are obtained with Mn values of 10 kg/mol or higher, as determined by solution NMR spectroscopy and gel permeation chromatography (GPC). The polymers PA P-5 to PA P-8 degrade prior to melting, whereas only PA P-10 shows melting on heating. The structural changes in the polymers, with increasing methylene segments, are investigated by X-ray diffraction and molecular modeling. Conformational changes as a function of temperature have been studied by solid-state NMR spectroscopy. These studies have been illustrative in following the phase transformations in the aromatic–aliphatic polymers. Fo...

Fermentation of aromatic lactate monomer and its polymerization to produce highly thermoresistant bioplastics

Microbial fermentation system is designed to convert glucose to 4-hydroxyphenyllactic acid (DHPA), an aromatic-containing derivatives of lactic acid. By a methylation, DHPA was transformed to a diol monomer to synthesize bio-based polyesters with benzene rings in their backbone. The polycondensation of DHPA diol was performed with a series of aliphatic diacid chlorides to produce semi-aromatic polyesters with glass-transition temperatures <45 °C. By polycondensation with aromatic diacylchlorides such as terephthaloyl chloride and isophthaloyl chloride, thermally stable DHPA-based polyesters with glass-transition temperatures as high as 130 °C were obtained.

Thermotropic liquid crystalline polyesters derived from bis-(4-hydroxybenzoyloxy)-2-methyl-1,4-benzene and aliphatic dicarboxylic acid chlorides

A series of thermotropic liquid crystalline polyesters derived from bis-(4-hydroxybenzoyloxy)-2- methyl-1,4-benzene (BHBOMB) and aliphatic dicarboxylic acid chlorides were investigated. All these polyesters were synthesized by interfacial polycondensation method and characterized by differential scanning calorimetry and wide-angle X-ray diffractometer. These polyesters consist of BHBOMB as a mesogenic diol and aliphatic diacid chlorides were used as flexible spacers. The length of oligomethylene units in polymer was varied from the trimethylene to the dodecamethylene groups. The transition temperatures and thermodynamic properties were studied for all these polymers. All these polyesters were soluble in chlorinated solvents such as chloroform, dichloromethane, dichloroethane, etc. More importantly, all these polyesters exhibited very large mesophase stability.

Synthesis and characterization of new soluble polyamides from Acenaphtohydrazinomercaptotriazole diamine

A diamine Acenaphtohydrazinomercaptotriazole (AHTD) was synthesized in one step from acenaphthoqinone and 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole. The diamin was characterized by FTIR, 1HNMR, 13CNMR and melting point. Diamin was used to prepare novel polyamides. The low temperature solution polycondensation of diamin with tow aromatic and tow aliphatic diacid chlorides afforded diamin-containing polyamides with inherent viscosities of 0.38–0.47 dl/g in DMF at 25 °C. The polyamides were generally soluble in a wide range of solvents such as dimethylformamide(DMF), N-Methylpyrolidone(NMP), tetrachloroethane (TCE), dimethylsulfoxide(DMSO) and H2SO4. Thermal analysis showed that these polyamides were practically crustily and with Tg under 100 °C.

New Polymer Syntheses Part 56: Novel Friedel-Crafts Polyketones Containing Naphthalene Moiety: Synthesis, Characterization and Antimicrobial Activity

Novel Friedel-Crafts polyketones containing naphthalene moiety were synthesized via the electrophilic Friedel-Crafts polycondensation method. The desired polyketones were obtained by the interaction of newly synthesized dinaphthylidenecycloalkanone monomers with different aliphatic and aromatic diacid chlorides. The structures of new monomers and polymers were confirmed by elemental and spectral analyses, besides X-ray single crystal data for the two new monomers. The new polyketones were characterized by solubility, viscometry, thermal properties, scanning electron microscopy and antimicrobial activity test. All the polyketones were soluble in formic acid as protonic solvent giving yellowish to brown colors. Some of the polyketones were partially soluble in n-hexane, benzene and chloroform. The thermal properties of those polymers were evaluated by TGA; DTG and DTA measurements. The desired polyketones have high thermal stability at T10 except polymer 3b which have low T10 value. FDT for all polyketones is nearly completed at around 522–677°C. The morphological properties of polyketone 2b were tested by SEM measurements. The synthesized monomers and polymers were screened for their antibacterial and antifungal activities. They showed a moderated antibacterial activity against tested Gram-negative and Gram-positive bacteria and no significant influence against the selected fungi species except monomer 1b and polymers 2a , 3b .

New Polyamides and Polyoxazoles Based on Diphenyl Ether Segments in the Polymers' Backbone

Two new series of polyamides, 7 a-e and polyoxazoles 8 a-e , containing diphenyl ether segments were synthesized using a low-temperature solution of polycondensation and polycyclization reactions, respectively. Polyamides were synthesized by interaction of monomer 4 with different aliphatic and aromatic diacid chlorides, including adipoyl, sebacoyl, oxaloyl, 4,4′-azodibenzoyl and 3,3′-azodibenzoyl dichlorides. The poly-merization reaction was carried out in dry DMF as a solvent and in the presence of anhydrous potassium carbonate as a catalyst at room temperature. Polyoxazoles were obtained as cyclization products form corresponding polyamides in polyphosphoric acid. The model compounds 5 and 6 were synthesized to know the optimum polymerization procedures. The structure of the model compounds as well as the resulting polymers was characterized by elemental and spectral analyses. The synthesized polymers were soluble in protonic solvents such as formic and concentrated sulfuric giving different colors. The thermal properties of those polymers were evaluated by TGA, DTG, and DTA measurements and correlated to their structural units. FDT for polyamides was nearly complete at around 730–750°C, while for polyoxazoles it was nearly complete at around 580–650°C. The glass transition temperatures for the selected polymers were in the range of 47–74°C, while T m values were in the range of 156–315°C. X-ray analysis showed that the selected polyamides have a higher degree of crystallinity than polyoxazoles in the region 2θ = 5−60°. In addition, the morphological properties of selected examples were tested by SEM measurements. A comparative SEM study was carried out between selected polyamides and polyoxazoles.

Polyamides with pendant 1,3,4-oxadiazole and pyridine moieties

A novel aromatic diamine, 2-(5-(3,5-diaminophenyl)-1,3,4-oxadiazole-2-yl)pyridine (POBD), containing a pyridine ring and a 1,3,4-oxadiazole moiety, was synthesized. It was used in a polycondensation with various aromatic and aliphatic diacid chlorides to generate a series of new aromatic polyamides with pendant 1,3,4-oxadiazole groups. The prepared polyamides were characterized by IR, elemental analysis and through the synthesis of model compounds. Thermophysical properties of the synthesized polyamides have been studied by DSC, TGA and inherent viscosity measurements. Relatively high inherent viscosity values (0.76–1.62 dL/g, in 0.125% H2SO4 at 25°C) were observed for these compounds. Number average molecular weight (Mn) of the polymers was measured by vapor phase osmometry (VPO). The introduction of bulky side chains in the structure of aromatic polyamides led to increased solubility of these polymers in common polar and aprotic solvents, such as DMF, DMSO, NMP and DMAc, which allowed thin films to be cast from polymer solutions. The highest molecular weight (Mn = 51190) was observed for polymer (IX), which was prepared from pyridine-2,6-dichlorocarbonyl.

Synthesis and characterization of new aliphatic polyesters containing dihydronaphthofuro[3,2-d]furan moiety

A dihydronaphthofuro[3,2-d]furan containing diol monomer, viz., 2,13-dihydroxy[7a,14c] dihydro naphtho[2,1-b]naphtho[1′,2′:4,5]furo[3,2-d] furan (DDNF) was synthesized in high yield and purity through the condensation of commercially available 2,7-dihydroxynaphthalene with glyoxal at room temperature. It was used as a new monomer for the synthesis of a series of novel dihydronaphthofuro-containing aliphatic polyesters by interfacial polycondensation method. Optimal conditions for polyesterification were obtained via study of the model compounds. The diol monomer and model compound were fully characterized by infrared, nuclear magnetic resonance (NMR), mass spectroscopies, and elemental analysis. Polyesters derived from DDNF and four aliphatic diacid chlorides had inherent viscosities ranging from 0.36 to 0.51 dL g−1. The chemical structure of the polymers was characterized by Fourier transform infrared, NMR spectroscopies and elemental analysis. The physical properties of the polymers were studied. The glass transition temperature was in the range of 89–118 °C. All the new polymers showed good thermal stability and very good solubility in most organic solvents.

Synthesis and characterization of new aliphatic polyesters containing methanodinaphtho[1,3]dioxocin part

AbstractA novel dinaphthodioxocin‐containing diol monomer, 8,16‐methano‐16H‐dinaphtho[2,1‐d:1′,2′‐g][1,3] dioxocin‐2,14‐diol (MDDD) was synthesized in high yield and purity through the condensation of 2,7‐dihydroxynaphthalene with malonaldehydetetramethyl acetal at room temperature. It is used as a new monomer for the synthesis of a series of novel dinaphthodioxocin‐containing aliphatic polyesters by interfacial polycondensation method. The new diol monomer was fully characterized by IR, NMR, mass spectroscopies, and elemental analysis. Optimal conditions for polyesterification were obtained via study of the model compounds. Polyesters derived from MDDD and four aliphatic diacid chlorides had inherent viscosities ranging from 0.26 to 0.38 dL/g. The chemical structure of the polymers was fully characterized by IR, NMR spectroscopies, and elemental analysis. The physical properties of the polymers were studied. All the new polymers show good thermal stability and very good solubility in most organic solvents. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

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°C, 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°C.

Synthesis and characterization of novel Schiff‐base polyamides from copper/benzil bisthiosemicarbazone complexes

AbstractA new copper‐containing Schiff‐base diamine, benzil bis(thiosemicarbazonato)copper(II) (CuLH4), was synthesized in two steps from benzil bisthiosemicarbazone (LH6). The ligand LH6 and the complex CuLH4 were characterized with Fourier transform infrared spectroscopy, 1H‐NMR, and elemental analysis. CuLH4 was used to prepare novel polyamides. The low‐temperature solution polycondensation of the complex CuLH4 with various aromatic and aliphatic diacid chlorides afforded copper‐containing Schiff‐base polyamides with inherent viscosities of 0.25–0.36 dL/g in N,N‐dimethylformamide (DMF) and 0.75 dL/g in H2SO4 at 25°C. The polyamides were generally soluble in a wide range of solvents, such as DMF, N,N‐dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, ethyl acetate, tetrachloroethane, hexamethylene phosphoramide, N‐methylpyrrolidone, and pyridine. Thermal analysis showed that these polyamides were practically amorphous, decomposed above 270°C, and exhibited 50% weight loss at and above 400°C. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

Ionic liquids as novel and green media for clean synthesis of soluble aromatic‐aliphatic poly(amide‐ester)s containing hydroxynaphthalene urazole moiety

AbstractIonic liquids (IL)s are very attractive and environmentally acceptable solvents. They can be used as green media for a number of chemical processes. In this investigation, for the advancement of ecological safety and improvement of technological ability of this process, room temperature ionic liquids (RTIL)s and quaternary ammonium salt, tetrabutylammonium bromide (TBAB) have been used both as an environmentally benign solvent and catalyst for the polycondensation 4‐(3‐hydroxynaphthalene)‐1,2,4‐triazolidine‐3,5‐dione (3HNTD) with aliphatic diacid chlorides, eliminating the need for a volatile organic solvent (VOS) and additional catalyst. The reaction of monomer 3HNTD with acetyl chloride was performed in N,N‐dimethylacetamide solution at different molar ratios, and the resulting mono‐, di‐, and trisubstituted derivatives were obtained in high yields and were finally used as models for polymerization reactions. The effects of various reaction parameters, such as the nature of the ILs, the amount of ILs, the reaction temperature, and the reaction time, on the yields and inherent viscosities of the resulting poly(amide‐ester)s (PAE)s were studied. Polycondensation reactions successfully proceeded in IL without any additional extra components, such as triethylamine or pyridine, which are used in similar reactions in organic solvents. Therefore, ILs can act both as solvent and catalyst. In addition to the solubility test, inherent viscosity as a measure of molecular weight was determined. PAEs were obtained in high yields with inherent viscosities ranging from 0.18 to 0.34 dl g−1. This method was also compared with conventional method for the synthesis of PAEs. Fluorimetric studies of the model compound as well as polymers were performed. Copyright © 2008 John Wiley &amp; Sons, Ltd.

Synthesis and Characterization of Poly(amide-ester)s Containing Naphthalene Pendent Groups and Urazole Rings

4-(3-Hydroxy-naphthalene)-1,2,4-triazolidine-3,5-dione (3HNTD) was synthesized in six steps starting from 3-hydroxy-2-naphthalene carboxylic acid. The reaction of monomer 3HNTD with acetyl chloride was performed in N,N-dimethylacetamide (DMAc) solution at different molar ratios, and the resulting mono-, di- and trisubstituted derivatives were obtained in high yields and were finally used as models for polymerization reactions. A series of novel aliphatic–aromatic poly(amide-ester)s (PAE)s containing a naphthalene pendent moiety were prepared from 3HNTD and various diacid chlorides (including succinyl chloride, adipoyl chloride and sebacoyl chloride) by polycondensation reactions with three methods: low-temperature solution polycondensation, solution polymerization under gradual heating and reflux conditions in the presence of pyridine and triethylamine as a proton scavenger and without a proton scavenger, respectively. PAEs from aliphatic diacid chlorides and 3HNTD have been studied in great detail via the conventional solution and their synthetic conditions have been optimized to achieve the highest possible molecular weights. In addition to the solubility test, inherent viscosity as a measure of molecular weight was determined. Structural characterization was performed by using infrared (IR), 1H-NMR spectroscopies and elemental analysis. Thermal properties were studied through thermogravimetic (TGA/DTG) thermal techniques. Fluorimetric and UV-Vis studies of the model compounds as well as polymers were performed.

Green Methodology with Ionic Liquids as a Media for Efficient Synthesis of Polyamides Derived from 4-(4-Dimethylaminophenyl)-1,2,4-triazolidine-3,5-dione and Diacid Chlorides2

Ionic liquids (ILs) represent a fascinating and potentially very valuable group of new solvents, which have the benefit of zero vapor pressure and therefore easier handling than many conventional solvents. They are attracting a lot of attention as volatile organic compound-free solvents, eco-friendly and green media. Room-temperature ionic liquids (RTILs) and particularly those based on substituted imidazolium cations, which can be synthesized easily from the commercially available starting material N-trimethylsilylimidazole and alkyl halides, are currently being extensively studied for a variety of applications. In this study a facile and efficient synthesis of heterocyclic polyamides by polycondensation of 4-(4-dimethylaminophenyl)-1,2,4-triazolidine-3,5-dione with various commercially available aliphatic diacid chlorides in the presence of RTILs and molten tetrabutylammonium bromide as an IL was performed. The effect of various reaction parameters, including the nature of the ILs, the amount of IL, the reaction temperature, and the reaction time were investigated to optimize the conditions for the preparation of heterocyclic polyamides. The polymerization proceeded well in ILs without any catalyst and polyamides were obtained with high yields and moderate inherent viscosities. A comparative study between the effects exerted by different ILs and the conventional polymerization method is also reported.

Novel ferrocene modified poly(amide ether amide)s and investigation of physical and thermal properties

A new diamine containing ferrocene group with preformed ether and amide units was prepared via reaction of 1,1′-ferrocenedicarbonyl chloride with two moles of 2,6-bis(5-amino-1-naphthoxy)pyridine. Polycondensation reactions of the prepared diamine with different aromatic and aliphatic diacid chlorides in the presence of trimethylchlorosilane (TMSCl) resulted in preparation of novel ferrocene modified poly(amide ether amide)s. The monomer and polyamides were characterized and the effect of trimethylchlorosilane (TMSCl) as activating agent on the polymerization reaction was studied. The physical and thermal properties of the polyamides including inherent viscosity, solubility, thermal stability and behavior, flame-retardancy and crystallinity of the polymers were studied. The polymers showed good thermal stability and flame-retardancy, and also improved solubility in polar aprotic solvents.

Novel Thermally Stable Poly(sulfone ether ester amide)s with Improved Solubility

AbstractA three-step method was used to prepare a novel sulfone ether ester diamine. In the first step, reaction of 1,5-dihydroxy naphthalene with 4- nitrobenzoyl chloride afforded 5-hydroxy-1-naphthyl-4-nitrobenzoate (HNNB). By reduction of nitro group, an amino compound named 5-hydroxyl-1-naphthyl- 4-aminobenzoate (HNAB) was obtained. Reaction of HNAB (two moles) with bis (4-chlorophenyl) sulfone resulted in preparation of a novel sulfone ether ester diamine (SEED). Polycondensation reactions of the diamine with aromatic and aliphatic diacid chlorides led to preparation of new poly(sulfone ether ester amide)s. Conventional methods were used to characterize the structure of the monomer and polymers. Physical properties of the polymers were also studied. The polyamides were thermally stable and they showed improved solubility in dipolar aprotic solvents.

HPLC analysis of aliphatic and aromatic dicarboxylic acid cross-linkers hydrolyzed from carbohydrate polyesters for estimation of the molar degree of substitution

Quantitative analysis of carboxylic acids in hydrophilic matrixes remains a challenge despite the introduction of derivatization reagents for carboxylic acids nearly three decades ago. Analysis of many bifunctional ester forming polymer cross-linkers are additionally complicated by the their amphiphatic character. We report a sensitive and selective HPLC method to quantify organic dicarboxylic acids resulting from the hydrolytic degradation of cross-linked carbohydrate polyesters. An important group of cross-linkers encompassing C 7–C 10 aromatic and non-chromophoric aliphatic diacid chlorides were investigated. Specific validation is reported for terephthalic acid, diethylmalonic acid and sebacic acid. Linear calibration curves were obtained in the 0.5–15.0 μg/ml range corresponding to a mass fraction of 0.05–1.5% diacid to polyester. The accuracy and precision in this range was 94.4–114.1 and 6.1–24.8% RSD, respectively. This method is suitable for the routine determination of the molar or mass degree of substitution in carbohydrate polyesters.

Novel diols containing ester and amide groups and resulting poly(ester amide ester)s

AbstractThe reaction of terephthaloyl chloride and 4‐hydroxybenzoic acid resulted in terephthalyl bis(4‐oxybenzoic) acid. This diester diacid was converted into its corresponding diester diacid chloride (terephthaloyl dioxydibenzoylchloride) via a reaction with thionyl chloride. Diols with preformed ester and amide groups were prepared through the reaction of terephthaloyl dioxydibenzoylchloride with 4‐aminophenol and 5‐amino‐1‐naphthol. Polycondensation reactions of the prepared diols with different aromatic and aliphatic diacid chlorides afforded eight aromatic and semiaromatic poly(ester amide ester)s. The polymers were fully characterized, and their physical and thermal properties were studied. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2699–2703, 2004

Novel pyridine-based ether ester diamine and resulting thermally stable poly (ether ester amide)s

A novel pyridine-based ether ester diamine was prepared in three steps. Reaction of 1,5-dihydroxy naphthalene with 4-nitrobenzoyl chloride afforded 5-hydroxy-1-naphthyl-4-nitrobenzoate (HNNB). Reduction of nitro group resulted in preparation of an amino compound named 5-hydroxyl-1-naphthyl-4-aminobenzoate (HNAB). The diamine was synthesized by nucleophilic substitution reaction of 5-hydroxyl-1-naphthyl-4-aminobenzoate with 2,6-dichloropyridine in the presence of K 2CO 3. The obtained diamine was fully characterized and used to prepare novel thermally stable poly (ether ester amide)s via polycondensation reaction with different aromatic and aliphatic diacid chlorides. All the polymers were characterized and their physical and thermal properties were studied.