Preparation and characterization of new photoactive polyamides containing 4‐(4‐dimethylaminophenyl)urazole units

4‐(4‐dimethylaminophenyl)‐1,2,4‐triazolidine‐3,5‐dione ( DAPTD ) was prepared from 4‐dimethylaminobenzoic acid in five steps. The compound DAPTD was reacted with excess acetyl chloride in N,N‐dimethylacetamide (DMAc) solution and gave 1,2‐bisacetyl‐4‐[4‐(dimethylaminophenyl)]‐1,2,4‐triazolidine‐3,5‐dione as a model compound. Solution polycondensation reactions of monomer with succinyl chloride (SucC), suberoyl chloride (SubC), and sebacoyl chloride (SebC) were performed under conventional solution polymerization techniques in the presence of triethylamine and pyridine as a catalyst in N‐methylpyrrolidone (NMP) and led to the formation of novel aliphatic polyamides. These novel polyamides have inherent viscosities in the range of 0.09–0.21 dL/g in N,N‐dimethylformamide (DMF) at 25°C. Fluorimetric studies of the model compound as well as polymers were performed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 947–954, 2007     

Synthesis of novel photoactive heterocyclic polyimides containing naphthalene moieties via cycloaddition reactions

1‐Naphthylacetic acid (1) was reacted with thionyl chloride and 1‐naphthyl‐ acetyl chloride (2) was obtained in a quantitative yield. The reaction of this acid chloride (2) with isoeugenol (3) was performed in chloroform and a novel isoeugenol ester derivative (4) as a monomer was obtained in a high yield. The compound (4) was characterized by ¹H‐NMR, IR, mass, and elemental analyses and then was used for the preparation of a model compound (6) and polymerization reactions. 4‐Phenyl‐1,2,4‐triazoline‐3,5‐dione (PhTD) (5) was allowed to react with compound (4). The reaction is very fast and gives only one double adduct (6) via Diels–Alder and ene pathways in an excellent yield. The polymerization reactions of the novel monomer (4) with bistriazolinediones [bis‐(p‐3,5‐dioxo‐1,2,4‐triazolin‐4‐ylphenyl)methane (7) and 1,6‐bis‐(3,5‐dioxo‐1,2,4‐triazolin‐4‐yl)hexane] (8) were carried out in N,N‐dimethylacetamide (DMAc) at room temperature. The reactions are exothermic and fast and gave novel heterocyclic polyimides containing a naphthalenic pendant group (9) and (10) via repetitive Diels–Alder‐ene polyaddition reactions. Stereochemical analysis of the model compound and fluorimetric studies of the model compound as well as polymers were done conclusively. Excimer formation of the polymers and its effect on fluorescence emission were investigated and some structural characterization and physical properties of these novel heterocyclic polyimides are reported. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 527–536, 2000     

Synthesis and characterization of novel optically active and flame‐retardant heterocyclic polyimides

Tetrachlorophthalic anhydride (1) was reacted with L ‐leucine (2) in toluene solution at refluxing temperature in the presence of triethylamine and the resulting imide‐acid (4) was obtained in quantitative yield. The compound (4) was converted to the N‐(tetrachlorophthaloyl)‐L ‐leucine acid chloride (5) by reaction with thionyl chloride. The reaction of this acid chloride (5) with isoeugenol (6) was carried out in chloroform and novel optically active isoeugenol ester derivative (7) as a chiral monomer was obtained in high yield. The compound (7) was characterized by ¹H‐NMR, IR, Mass and elemental analysis, and then was used for the preparation of model compound (10) and polymerization reactions. 4‐Phenyl‐1,2,4‐triazoline‐3,5‐dione, PhTD (8) was allowed to react with compound (7). The reaction is very fast, and gives only one diastereomer of (10) via Diels–Alder and ene pathways in excellent yield. The polymerization reactions of novel monomer (7) with bistriazolinediones [bis‐(p‐3,5‐dioxo‐1,2,4‐triazolin‐4‐ylphenyl)methane (11) and 1,6‐bis‐(3,5‐dioxo‐1,2,4‐triazolin‐4‐yl)hexane] (12) were carried out in N,N‐dimethylacetamide (DMAc) at room temperature. The reactions are exothermic, fast, and give novel optically active polymers (13) and (14) via repetitive Diels–Alder‐ene polyaddition reactions. The resulting polymers are optically active, thermally stable, and flame resistant. All of the above compounds were fully characterized by IR, ¹H‐NMR, elemental analysis, and specific rotation. Some structural characterization and physical properties of these novel heterocyclic polyimides are reported. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 240–248, 2000     

Synthesis and characterization of novel polyimides containing triazoles units in the main chain by click chemistry

In this study, some polyimides containing triazoles units in the main chain was prepared from the polymerization of dialkynes including imide linkages and diazides in the presence of Cu (I) catalyst in yield of 76.2–87.6%, with inherent viscosity of 0.37–0.53 dL g^?1. The obtained polymers are soluble in polar aprotic solvents such as N,N‐dimethyformamide (DMF), N,N‐dimethyacetamide (DMAc), dimethyl sulfoxide (DMSO), and N‐methyl‐2‐pyrrolidone (NMP). These polymers were characterized using FT‐IR, ¹H‐NMR, and elemental analysis techniques. Their thermal stability was evaluated with thermogravimetric (TGA) analysis and differential scanning calorimetry (DSC) techniques under a nitrogen atmosphere which is indicative of their good thermal stability. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of a rigid poly(amide hydrazide): effect of some reaction parameters on the viscosity of the polymer formed

A wholly aromatic all-para oriented poly(amide hydrazide) has been synthesized from N,N′-bis(4-aminobenzoyl) hydrazine (BABH) and terephthaloyl chloride (TC) by low temperature solution polycondensation. The polymer was characterized by elemental analyses, IR spectroscopy, solubility, viscosity and density measurements. The effect of various factors controlling the polymerization reaction (concentration of monomer and electrolyte (LiCl) in the reaction medium, nature of the medium and temperature at the initial stage of polymerization) on polymer viscosity was studied. To prepare a polymer of high viscosity, the optimum conditions were found to be, monomer concentration 0·25moll^-1, LiCl concentration (in DMAc) 1% (w/v), with use of N-methyl pyrrolidone (NMP) as polymerization medium. The thermal behaviour of the polymer was studied in air and nitrogen by TGA and DSC. ©1997 SCI     

Highly diastereoselective synthesis of novel polymers via tandem Diels–Alder–ene reactions

Cis -9,10-dihydro-9,10-ethanoanthracene-11-12-dicarboxylic acid anhydride (1) was converted into its amic acid derivative by reaction with L -leucine. The cyclization reaction was carried out in situ using triethylamine to give the succinic imide-acid derivative (2). Compound (2) was converted to the acid chloride (3) by reaction with thionyl chloride. The reaction of acid chloride (3) with isoeugenol (4) was carried out in chloroform and a novel optically active isoeugenol ester derivative (5) was obtained in high yield. 4-Phenyl-1,2,4-triazoline-3,5-dione (PhTD) (6) was allowed to react with compound (5). The reaction is very fast and gives only one diastereoisomer of (7) via Diels–Alder and ene pathways in quantitative yield. Compound (7) was characterized by ¹H NMR, IR, specific rotation and elemental analysis, and was used as a model for the polymerization reactions. The polymerization reactions of compound (5) with bis-triazolinediones (8), (9) were performed in N,N-dimethylacetamide (DMAc) at room temperature. The reactions are exothermic and fast, and give novel optically active polymers. Some physical properties and structural characterizations of these new polymers have been studied, and are reported. © 1999 Society of Chemical Industry     

Microwave‐assisted rapid polycondensation reaction of 4‐(4′‐acetamidophenyl)‐1,2,4‐triazolidine‐3,5‐dione with diisocyanates

4‐(4′‐Aminophenyl)‐1,2,4‐triazolidine‐3,5‐dione was reacted with 1 mol of acetyl chloride in dry N,N‐dimethylacetamide (DMAc) at ?15°C and 4‐(4′‐acetamidophenyl)‐1,2,4‐triazolidine‐3,5‐dione [4‐(4′‐acetanilido)‐1,2,4‐triazolidine‐3,5‐dione] (APTD) was obtained in high yield. The reaction of the APTD monomer with excess n‐isopropylisocyanate was performed at room temperature in DMAc solution. The resulting bis‐urea derivative was obtained in high yield and was finally used as a model for the polymerization reaction. The step‐growth polymerization reactions of monomer APTD with hexamethylene diisocyanate, isophorone diisocyanate, and tolylene‐2,4‐diisocyanate were performed under microwave irradiation and solution polymerization in the presence of pyridine, triethylamine, or dibutyltin dilaurate as a catalyst. Polycondensation proceeded rapidly, compared with conventional solution polycondensation; it was almost completed within 8 min. The resulting novel polyureas had an inherent viscosity in the range of 0.07–0.17 dL/g in dimethylformamide or sulfuric acid at 25°C. These polyureas were characterized by IR, ¹H‐NMR, elemental analysis, and thermogravimetric analysis. The physical properties and structural characterization of these novel polyureas are reported. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2103–2113, 2004     

Synthesis and characterization of poly(vinyl chloride‐co‐vinyl acetate)‐graft‐poly[(meth)acrylates] by atom transfer radical polymerization

The graft polymerization of methyl methacrylate and butyl acrylate onto poly(vinyl chloride‐co‐vinyl acetate) with atom transfer radical polymerization (ATRP) was successfully carried out with copper(I) thiocyanate/N,N,N′,N′,N″‐pentamethyldiethylenetriamine and copper(I) chloride/2,2′‐bipyridine as catalysts in the solvent N,N‐dimethylformamide. For methyl methacrylate, a kinetic plot of ln([M]₀/[M]) (where [M]₀ is the initial monomer concentration and [M] is the monomer concentration) versus time for the graft polymerization was almost linear, and the molecular weight of the graft copolymer increased with increasing conversion, this being typical for ATRP. The formation of the graft polymer was confirmed with gel permeation chromatography, ¹H‐NMR, and Fourier transform infrared spectroscopy. The glass‐transition temperature of the copolymer increased with the concentration of methyl methacrylate. The graft copolymer was hydrolyzed, and its swelling capacity was measured. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 183–189, 2005     

Chromophoric poly(urea‐urethane)s with pendent 3‐hydroxynaphthalene group: Synthesis and characterization

The reaction of 4‐(3‐hydroxynaphthalene)‐1,2,4‐triazolidine‐3,5‐dione ( 3HNTD ) with n‐propylisocyanate was performed at different molar ratios. The resulting monosubstituted urea and disubstituted urea‐urethane derivatives were obtained in high yields and were used as model compounds for polymerization reactions. 3HNTD as a monomer was used in the preparation of heterocyclic poly(urea‐urethane)s to produce photoactive polymers, by polycondensation with different diisocyanates in N,N‐dimethylacetamide (DMAc) solution. Chromophoric heterocyclic polymers containing naphthalene group, obtained in quantitative yields, possessed inherent viscosities in the range of 0.14–0.38 dL/g. The resulting poly(urea‐urethane)s is insoluble in most organic solvents, but easily soluble in polar solvents such as dimethyl sulfoxide (DMSO), DMAc, and N‐methylpyrrolidone (NMP). The polymers were characterized by IR, ¹H‐NMR, elemental analysis, and TGA. Fluorimetric and UV–vis studies of the monomer as well as polymers were performed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of Photoactive Polyureas Derived from 4-(4-Dimethylaminophenyl)-1,2,4-triazolidine-3,5-dione and Diisocyanates

Summary 4-(4-Dimethylaminophenyl)-1,2,4-triazolidine-3,5-dione (DAPTD) was prepared from 4-dimethylaminobenzoic acid in five steps. The reaction of monomer DAPTD with n-isopropylisocyanate was performed at room temperature in N,N-dimethylacetamide (DMAc) solution and the resulting bis-urea derivative was obtained in high yield and was finally used as a model compound for polymerization reaction. The step-growth polymerization reactions of monomer with hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI) and toluene-2,4-diisocyanate (TDI) were performed in DMAc solution in the presence of pyridine, triethylamine or dibutyltin dilurate as catalysts. Some physical properties and structural characterization of these novel polyureas are reported. Fluorimetric studies of the model compound as well as polymers were performed.     

Synthesis of novel heterocyclic polyimides containing trimellitimide acid moieties

4‐Nitrobezoyl chloride (2) was reacted with isoeugenol in chloroform in the presence of triethyl amine and ester (4) was obtained in high yield. Ester (4) was reacted with SnCl₂·2H₂O to give amine‐ester (5), and subsequently was reacted with trimellitic anhydride (6) and novel isoeugenol ester‐imide derivative (7), as a new monomer was obtained in quantitative yield. Compound (7) was characterized by high‐field ¹H–NMR, IR, and elemental analysis and then was used for the preparation of model compound (9) and polymerization reactions. 4‐Phenyl‐1,2,4‐triazoline‐3,5‐dione (PhTD) (8) was allowed to react with compound (7). The reaction is very fast and gives only one double adduct (9) via Diels–Alder and ene pathways in excellent yield. The polymerization reactions of novel monomer (7) with bistriazolinediones [bis(p‐3,5‐dioxo‐1,2,4‐triazolin‐4‐ylphenyl)methane (10) and 1,6‐bis(3,5‐dioxo‐1,2,4‐triazolin‐4‐yl)hexane (11)] were carried out in N,N‐dimethylacetamide (DMAc) at room temperature. The reactions are exothermic, fast, and gave novel heterocyclic polyimides (12) and (13) via repetitive Diels–Alder‐ene polyaddition reactions. Some structural characterization and physical properties of these novel heterocyclic polyimides are reported. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1716–1725, 2001     

Direct Controlled Polymerization of Ionic Monomers by Surface-Initiated ATRP Using a Fluoroalcohol and Ionic Liquids

Surface-initiated atom transfer radical polymerization (ATRP) of (2-methacryloyloxyethyl)trimethylammonium chloride (MTAC), 3-(N-2-methacryloyloxyethyl-N,N-dimethyl) ammonatopropanesulfonate) (MAPS), and 2-methacryloyloxyethyl phosphorylcholine (MPC) was carried out in 2,2,2-trifluoroethanol (TFE) containing a small amount of 1-hexyl-3-methylimidazolium chloride at 60 °C to produce well-defined ionic polymer brushes and the corresponding free polymers with predictable number-average molecular weight (M_n, 1×10⁴−3×10⁵ g mol⁻¹) and narrow molecular weight dispersity (M_w/M_n<1.2). A first-order kinetic plot for ATRP of MTAC and MAPS revealed a linear relationship between the monomer conversion index (ln([M]₀/[M])) and polymerization time. Reduction in polymerization rates was observed with an increase in ionic liquid concentration. The M_n of both poly(MTAC) and poly(MAPS) increased in proportion to the conversion. The sequential polymerization of MAPS initiated with the chain ends of poly(MAPS) produced the postpolymer with quantitative efficiency. The thickness of the polymer brush was controllable from 5 to 100 nm based on the M_n of the polymer. These results suggest the successful control of the polymerization of sulfobetaine-type methacrylates owing to the TFE and ionic liquids. In particular, the high affinity of TFE for the sulfobetaine monomers and polymers yielded a homogeneous polymerization media to improve surface-initiated polymerization generating the polymer brushes on the substrate surface as well as the free polymers formed in the solution. The effect on ATRP of the chemical structure of ionic liquids and ligands for copper catalyst was also investigated.     

Synthesis of perfluorohexyl‐terminated poly(ethylene oxide) using maghnite‐h as clay catalyst

Activated monomer cationic ring‐opening polymerization of ethylene oxide initiated with 1H,1H,2H, 2H‐perfluorooctan‐1‐ol, using acid exchanged montmorillonite clay called Maghnite‐H⁺ (Mag‐H⁺) as an effective catalyst, was carried out to obtain the corresponding homopolymers with narrow polydispersity ratios. The molecular weights of the obtained polymers could be controlled with the feed ratio of the monomer and initiator. The effect of amount of catalyst and time on the polymerization yield and viscosity of the polymers were studied. The structure was confirmed by ¹H‐NMR and MALDI‐TOF‐MS. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of new polyamides derived from 4‐(4′‐aminophenyl)urazole and aliphatic diacid chlorides

4‐(4′‐Aminophenyl)urazole (AmPU) was prepared from 4‐nitrobenzoic acid in six steps. The reaction of AmPU with acetyl chloride was performed in N,N‐dimethylacetamide solutions at different ratios, and the resulting disubstituted and trisubstituted amide derivatives were obtained in high yields and were used as models for polymerization reactions. Polycondensation reactions of AmPU with succinyl chloride, suberoyl chloride, and sebacoyl chloride were performed with conventional solution polymerization techniques in the presence of different catalysts, such as pyridine, triethylamine, and dibutyltin dilaurate, and led to the formation of novel aliphatic polyamides. The resulting novel polyamides had inherent viscosities of 0.11–0.22 dL/g in dimethylformamide or H₂SO₄ at 25°C. These polyamides were characterized with IR, ¹H‐NMR, elemental analysis, and thermogravimetric analysis. Some physical properties and structural characterization of these novel polyamides are reported. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3173–3185, 2004     

Synthesis,X-ray structure,and polymerization of 1-vinyl-3-cyanomethylimidazolium chloride

A new monomer, 1-vinyl-3-cyanomethylimidazolium chloride (1), was synthesized via quaternization of 1-vinylimidazole with chloroacetonitrile. The monomer was characterized using ¹H– and ¹³C–NMR as well as Raman spectroscopic techniques; its crystal structure was studied by means of X-ray analysis. The radical polymerization of 1 in aqueous solution brought about the formation of a polyelectrolyte that retains cyano groups intact and possesses film-forming properties. The structure of the polymer was characterized by NMR and Raman spectroscopy. The high viscosity of aqueous solutions and chemical structure of the polymer obtained suggest its possible applications as a thickener and/or detergent additive. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 499–509, 2001     

Synthesis and characterization of a novel hyperbranched polyether

A hyperbranched polyether has been synthesized by a single‐step nucleophilic displacement polymerization technique between cyanuric chloride and the sodium salt of bisphenol‐A. The effects of various reaction parameters on the yield, and molecular weight, as measured by the intrinsic viscosity of the polymer, have been studied. The synthesized polymer has been characterized by FT‐IR, UV and ¹H NMR spectroscopies, elemental analysis, solubility and viscosity measurements. The polymer is soluble in highly polar solvents such as N,N‐dimethylacetamide, N,N‐dimethylformamide and dimethyl sulfoxide, partially soluble in dilute aqueous NaOH solution, methanol, ethanol, chloroform, etc., but insoluble in water and non‐polar hydrocarbon solvents. The solubility parameter of the hyperbranched polymer has also been measured experimentally. Copyright © 2004 Society of Chemical Industry     

Synthesis of soluble and thermally stable polyamides from diamine containing (quinolin‐8‐yloxy) aniline pendant group

A novel diamine monomer having pendant 4‐(quinolin‐8‐yloxy) aniline group was successfully synthesized via aromatic substitution reaction of 8‐quinolinol with p‐fluoronitrobenzene followed by Pd/C catalyzed hydrazine reduction, amidation reaction between 4‐(quinolin‐8‐yloxy) aniline and 3,5‐dinitrobenzoylcholoride followed by Pd/C catalyzed hydrazine reduction. The diamine monomer was fully characterized by using FTIR, ¹H‐NMR, ¹³C‐NMR, and elemental analysis. The diamine monomer was polymerized with various aromatic and aliphatic dicarboxylic acids to obtain the corresponding polyamides. The polyamides had inherent viscosity in the range of 0.30–0.41 dL/g and exhibited excellent solubility in the polar aprotic solvents such as DMAc, NMP, N,N‐dimethylformamide, Pyridine, and DMSO. The glass transition temperatures (T_g) of the polymers are high (up to 313°C) and the decomposition temperatures (T_i) range between 200 and 370°C, depending on the diacids residue in the polymers backbone. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Free radical kinetics of N‐methyl N‐vinyl acetamide polymerization at low conversions in aqueous media

N‐methyl N‐vinyl acetamide (NMNVA) monomer was polymerized at low conversions and its free radical kinetics were detailed using capillary dilatometry. The polymerizations were conducted isothermally, at 40°C using 2,2′‐azobis[2‐(2‐imidazolin‐2‐yl) propane dihydrochloride] (ABDH) as initiator. Monomer concentration and initiator concentration ranges were 1.10–1.70 mol · L⁻¹ and 1–4 mmol · L⁻¹, respectively. The aqueous polymerization media were kept at neutral pH. The rates of polymerization (R_p) and orders of reaction with respect to NMNVA and ABDH concentrations were evaluated and the kinetic expression was found to be ideal, with R_p ∝ [NMNVA]^1.07 [ABDH]^0.61. The polymers obtained were characterized by their viscosity numbers and correlation of viscosity average molecular weights was made with the amount of ABDH initiator. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 337–341, 2001     

Ultrasonically initiated emulsion polymerization of n‐butyl acrylate

Ultrasonically initiated emulsion polymerization of n‐butyl acrylate (BA) without added initiator has been studied. The experimental results show that high conversion of BA can be reached in a short time by employing an ultrasonic irradiation technique with a high purge rate of N₂. The viscosity average molecular weight of poly(n‐butyl acrylate) (PBA) obtained reaches 5.24 × 10⁶ g mol^?1. The ultrasonically initiated emulsion polymerization is dynamic and complicated, with polymerization of monomer and degradation of polymer occurring simultaneously. An increase in ultrasound intensity leads to an increase in polymerization rate in the range of cavitation threshold and cavitation peak values. Lower monomer concentration favours enhancement of the polymerization rate. ¹H NMR, ¹³C NMR and FTIR spectroscopies reveal that there are some branches and slight crosslinking, and also carboxyl groups in PBA. Ultrasonically initiated emulsion polymerization offers a new route for the preparation of nanosized latex particles; the particle size of PBA prepared is around 50–200 nm as measured by transmission electron microscopy. © 2001 Society of Chemical Industry     

Synthesis and characterization of new polyureas derived from 4‐(4′‐Methoxyphenyl)urazole

4‐(4′‐Methoxyphenyl)urazole (MPU) was prepared from 4‐methoxybenzoic acid in five steps. The reaction of monomer MPU with n‐isopropylisocyanate was performed at room temperature in N,N‐dimethylformamide solution, and the resulting bis‐urea derivative was obtained in high yield and was finally used as a model for polymerization reaction. The step‐growth polymerization reactions of monomer MPU with hexamethylene diioscyanate, isophorone diioscyanate, and toluene‐2,4‐diioscyanate were performed in N,N‐dimethylacetamide solution in the presence of pyridine as a catalyst. The resulting novel polyureas have an inherent viscosity (η_inh) in a range of 0.07–0.21 dL/g in DMF and sulfuric acid at 25°C. These polyureas were characterized by IR, ¹H‐NMR, elemental analysis, and TGA. Some physical properties and structural characterization of these novel polyureas are reported. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1141–1146, 2002