Efficient and rapid synthesis of optically active polyamides in the presence of tetrabutylammonium bromide as ionic liquids under microwave irradiation

There is increasing interest in using ionic liquids (ILs) as solvents for polymerization processes. The use of an inexpensive and readily available IL such as tetrabutylammonium bromide (TBAB) as a solvent for clean synthesis and catalytic processes is becoming widely recognized and accepted. This article reports an extension of a microwave method, describing the synthesis of optically active polyamides (PAs) in TBAB. Polycondensation reactions of diacid 5‐(3‐methyl‐2‐phthalimidylpentanoylamino) isophthalic acid with different diisocyanates such as 4, 4′‐methylenebis(phenyl isocyanate), toluylene‐2,4‐diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate were carried out in the presence of TBAB as a molten salt under microwave irradiation and with a conventional heating method, and they were compared with polymerizations in a traditional solvent such as 1‐methyl‐2‐pyrrolidone. A series of optically active PAs with high yields and inherent viscosities ranging from 0.20 to 0.60 dL/g were obtained. These PAs were characterized with Fourier transform infrared spectroscopy, specific rotation measurements, ¹H‐NMR, elemental analysis, thermogravimetric analysis, and differential scanning calorimetry. All data agreed with the proposed structures. Some physical properties and structural characterizations of these PAs are reported. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of thermostable chiral extended polyamides bearing N‐phthaloyl‐L‐leucine pendent architectures in green media

Ionic liquids (ILs) are often well‐known benign solvents capable of replacing conventional organic solvents, and they have become attractive solvents for many chemical reactions. Aromatic polyamides (PAs) have received particular interest in past years because of their high thermal and chemical resistance and their potential as high‐performance materials for different applications. In this investigation, the preparation of extended PAs derived from 5‐aminoisophthalic acid containing chiral pendent linkage (N‐phthaloyl‐L ‐leucine) with various aromatic diamines was studied. The bulky monomer 5‐(4‐methyl‐2‐phthalimidylpentanoylamino)isophthalic acid was prepared in three steps. Direct polyamidation of this monomer with several commercially available diamines in the presence of IL (1,3‐dipropylimidazolium bromide) and triphenyl phosphite gave novel PAs in good yields and inherent viscosities in the range of 0.38–0.55 dL g^?1. Because of the existence of amino acid in this architect, the resulting polymers are optically active. All of these PAs showed good solubility and readily dissolved in many organic solvents. Characterization of all the products was performed by FTIR, specific rotation, and representative ones by ¹H NMR, elemental analysis, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). TGA exhibited that two elite polymers were stable, with 10% weight loss recorded above 410 and 430°C in the nitrogen atmosphere. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Microwave‐assisted and classical heating polycondensation reaction of bis(p‐amido benzoic acid)‐N‐trimellitylimido‐L‐leucine with diisocyanates as a new method for preparation of optically active poly(amide imide)s

A new class of optically active poly(amide imide)s were synthesized via direct polycondensation reaction of diisocyanates with a chiral diacid monomer. The step‐growth polymerization reactions of monomer bis(p‐amido benzoic acid)‐N‐trimellitylimido‐L‐leucine (BPABTL) (5) as a diacid monomer with 4,4′‐methylene bis(4‐phenylisocyanate) (MDI) (6) was performed under microwave irradiation, solution polymerization under gradual heating and reflux condition in the presence of pyridine (Py), dibuthyltin dilurate (DBTDL), and triethylamine (TEA) as a catalyst and without a catalyst, respectively. The optimized polymerization conditions according to solvent and catalyst for each method were performed with tolylene‐2,4‐diisocyanate (TDI) (7), hexamethylene diisocyanate (HDI) (8), and isophorone diisocyanate (IPDI) (9) to produce optically active poly(amide imide)s by the diisocyanate route. The resulting polymers have inherent viscosities in the range of 0.09–1.10 dL/g. These polymers are optically active, thermally stable, and soluble in amide type solvents. All of the above polymers were fully characterized by IR spectroscopy, ¹H NMR spectroscopy, elemental analyses, specific rotation, and thermal analyses methods. Some structural characterization and physical properties of this new optically active poly(amide imide)s are reported. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1647–1659, 2004     

Polymerization of 4‐(4′‐N‐1,8‐naphthalimidophenyl)‐1,2,4‐triazolidine‐3,5‐dione with diisocyanates

4‐(4′‐Aminophenyl)‐1,2,4‐triazolidine‐3,5‐dione ( 1 ) was reacted with 1,8‐naphthalic anhydride ( 2 ) in a mixture of acetic acid and pyridine (3 : 2) under refluxing temperature and gave 4‐(4′‐N‐1,8‐naphthalimidophenyl)‐1,2,4‐triazolidine‐3,5‐dione ( NIPTD ) ( 3 ) in high yield and purity. The compound NIPTD was reacted with excess n‐propylisocyanate in N,N‐dimethylacetamide solution and gave 1‐(n‐propylamidocarbonyl)‐4‐[4′‐(1,8‐naphthalimidophenyl)]‐1,2,4‐triazolidine‐3,5‐dione ( 4 ) and 1,2‐bis(n‐propylamidocarbonyl)‐4‐[4′‐(1,8‐naphthalimidophenyl)]‐1,2,4‐ triazolidine‐3,5‐dione ( 5 ) as model compounds. Solution polycondensation reactions of monomer 3 with hexamethylene diisocyanate ( HMDI ), isophorone diisocyanate ( IPDI ), and tolylene‐2,4‐diisocyanate ( TDI ) were performed under microwave irradiation and conventional solution polymerization techniques in different solvents and in the presence of different catalysts, which led to the formation of novel aliphatic‐aromatic polyureas. The polycondensation proceeded rapidly, compared with conventional solution polycondensation, and was almost completed within 8 min. These novel polyureas have inherent viscosities in a range of 0.06–0.20 dL g^?1 in conc. H₂SO₄ or DMF at 25°C. Some structural characterization and physical properties of these novel polymers are reported. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2861–2869, 2003     

Synthesis of novel azo‐containing polyureas derived from 4‐[4′‐(2‐hydroxy‐1‐naphthylazo)phenyl]‐1,2,4‐triazolidine‐3,5‐dione

4‐[4′‐(2‐Hydroxy‐1‐naphthylazo)phenyl]‐1,2,4‐triazolidine‐3,5‐dione ( HNAPTD ) ( 1 ) has been reacted with excess amount of n‐propylisocyanate in DMF (N,N‐dimethylformamide) solution at room temperature. The reaction proceeded with high yield, and involved reaction of both N? H of the urazole group. The resulting bis‐urea derivative 2 was characterized by IR, ¹H‐NMR, elemental analysis, UV‐Vis spectra, and it was finally used as a model compound for the polymerization reaction. Solution polycondensation reactions of monomer 1 with Hexamethylene diisocyanate ( HMDI ) and isophorone diisocyanate ( IPDI ) were performed in DMF in the presence of pyridine as a catalyst and lead to the formation of novel aliphatic azo‐containing polyurea dyes, which are soluble in polar solvents. The polymerization reaction with tolylene‐2,4‐diisocyanate ( TDI ) gave novel aromatic polyurea dye, which is insoluble in most organic solvents. These novel polyureas have inherent viscosities in a range of 0.15–0.22 g dL^?1 in DMF at 25°C. Some structural characterization and physical properties of these novel polymers are reported. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3177–3183, 2001     

Microwave assisted glycolysis of poly(ethylene terephthalate) catalyzed by 1‐butyl‐3‐methylimidazolium bromide ionic liquid

The combination of ionic liquid (IL) associated with microwave energy may have some potential application in the chemical recycling of poly (ethylene terephthalate). In this processes, glycolysis of waste poly (ethylene terephthalate) recovered from bottled water containers were thermally depolymerized with solvent ethylene glycol (EG) in the presence of 1‐butyl‐3‐methyl imidazolium bromide ([bmim]Br) as catalyst (IL) under microwave condition. It was found that the glycolysis products consist of bis (2‐hydroxyethyl) terephthalate (BHET) monomer that separated from the catalyst IL in pure crystalline form. The conversion of PET reach up to 100% and the yield of BHET reached 64% (wt %). The optimum performance was achieved by the use of 1‐butyl‐3‐methyl imidazolium bromide as a catalyst, microwave irradiations temperature (170–175°C) and reaction time 1.75–2 h. The main glycolysis products were analyzed by ¹H NMR, ¹³C NMR, LC‐MS, FTIR, DSC, and TGA. When compared to conventional heating methods, microwave irradiation during glycolysis of PET resulted in short reaction time and more control over the temperature. This has allowed substantial saving in energy and processing cost. In addition, a more efficient, environmental‐friendly, and economically feasible chemical recycling of waste PET was achieved in a significantly reduced reaction time. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41666.     

Synthesis and characterization of new polyureas based on 4‐(4′‐aminophenyl)urazole and various diisocyanates

4‐(4′‐Aminophenyl)urazole (AmPU) was prepared from 4‐nitrobenzoic acid in six steps. The reaction of monomer AmPU with n‐isopropylisocyanate was performed in N,N‐dimethylacetamide solutions at different ratios, and the resulting disubstituted and trisubstituted urea derivatives were obtained in high yields and were finally used as models for polymerization reactions. The step‐growth polymerization reactions of AmPU with hexamethylene diisocyanate, isophorone diisocyanate, and toluene‐2,4‐diisocyanate were performed in N‐methylpyrrolidone solutions in the presence of pyridine as a catalyst. The resulting novel polyureas had inherent viscosities of 0.11–0.18 dL/g in dimethylformamide at 25°C. These polyureas were characterized with IR, ¹H‐NMR, elemental analysis, and thermogravimetric analysis. Some physical properties and structural characterization of these novel polyureas are reported. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2692–2700, 2003     

Straightforward and green method for the synthesis of nanostructure poly(amide-imide)s-containing benzimidazole and amino acid moieties by microwave irradiation

Owing to unique advantages such as shorter reaction times, higher yields, limited generation of by-products, and relatively easy scale-up without detrimental effects, microwave (MW)-assisted polymer synthesis has become an interesting synthetic tool. Also, the usage of ionic liquids (ILs) as perfect “MW solvents” has opened up a new research area among MW-assisted polymerizations. In this investigation, an attempt is made to synthesize several chiral nanostructure poly(amide-imide)s (PAIs) via fast, green, and simple polymerization reaction of several amino acid-based chiral diacids with an aromatic diamine, 2-(3,5-diaminophenyl)-benzimidazole, in tetrabutylammonium bromide as a molten IL under MW irradiation. Organo-soluble and high-performance PAIs were synthesized with high yields and inherent viscosities in the range of 0.40–0.52 dL g^?1. These obtained PAIs were characterized using Fourier-transform infrared spectroscopy, specific rotation measurements, X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), thermogravimetric analysis, and ¹H-NMR spectra techniques. The FE-SEM micrographs and XRD showed that the synthesized PAIs were nanostructure and amorphous polymers. To see the efficiency of MW irradiation conjugated with IL, this method was compared with polycondensation under conventional heating method. The combined merits of MW irradiation and IL make the polycondensation reactions with safe operation, low pollution, rapid access to products, and simple workup.     

Synthesis of new polyureas derived from 4‐cyclohexylurazole

4‐Cyclohexylurazole (1) R = cyclohexyl (CHU) was prepared from cyclohexyl isocyanate in two steps. Polycondensation reactions of compound CHU with hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), and toluene‐2,4‐diisocyanate (TDI) were performed in DMAc/chloroform and DMAC in the presence of pyridine as a catalyst. The resulting novel polyureas have an inherent viscosity in the range of 0.044–0.206 g/dL in DMF at 25°C. These polyureas were characterized by IR, ¹H–NMR, elemental analysis, and TGA. The resulting polymers are soluble in most organic solvents. Some physical properties and structural characterization of these novel polyureas are reported. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1335–1341, 2001     

Rapid synthesis of new block copolyurethanes derived from L‐leucine‐PEG in ionic liquids under microwave irradiation

This study concerns the synthesis of novel multi block polyurethane (PU) copolymers containing eco‐friendly segments, taking the advantage of ionic liquids (IL)s under microwave irradiation. For this, L ‐leucine anhydride cyclodipeptide (LAC) was prepared and then a new class of poly(ether‐urethane‐urea)s (PEUUs) was synthesized with two types of ILs, including room temperature imidazolium (RTIL)s and molten ammonium type ILs. ILs were used as reaction media and PUs were prepared via two‐step polymerization method. Polymerization reaction was also conducted under conventional heating method in N‐methyl pyrrolidone (NMP) as reaction solvent. In the first step, 4,4′‐methylene‐bis(4‐phenylisocyanate) (MDI) was reacted with LAC to produce isocyanate‐terminated poly(imide‐urea) oligomers as hard segment. Chain extension of the resulting prepolymer with polyethyleneglycol (PEG) of molecular weights of 400 (PEG‐400) was the second step to furnish a series of new PEUUs. These multiblock copolymers are optically active, thermally stable and soluble in amide‐type solvents. PEUUs prepared in ILs under microwave irradiation showed more phase separation and crystallinity than PEUU prepared under conventional method. Some structural characterization and physical properties of these PEUUs, prepared under different methods, are reported and compared. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of new heat-resistant polyamides bearing an <Emphasis Type="Italic">s</Emphasis>-triazine ring under green conditions

In this work, cyanuric chloride was reacted with morpholine to obtain 2,4-dichloro-6-morpholino-1,3,5-triazine, which was then reacted with 4-aminobenzoic acid, yielding a new triazine monomer containing dicarboxylic acid. The chemical structure and purity of this monomer was confirmed by different techniques. Direct polycondensations of this diacid with several aromatic diamines were carried out in a molten ionic liquid, tetrabutylammonium bromide. Polyamides (PAs) with moderate inherent viscosities in the range 0.32–0.38 dL g^?1 were obtained in high yields. These PAs were characterized by Fourier transform infrared spectroscopy, ¹H NMR spectroscopy, X-ray powder diffraction, inherent viscosity measurements, and elemental analysis. All of the PAs were found to be amorphous, to possess outstanding solubilities, and to be easily dissolved in amide-type polar aprotic solvents. The thermal properties of the PAs were evaluated by thermogravimetric analysis and differential scanning calorimetry. These polymers showed good thermal stability with glass transition temperatures (T _g) of 223–248°C, and their 10% weight loss temperatures were around 448°C and 460°C, confirming their good thermal stability. The char yields of these polymers were 53–59%, and, given their LOI values of 39–41, these polymers also show good flame retardancy.     

Microwave‐irradiated ring‐opening polymerization of D,L‐lactide under atmosphere

Poly(D ,L ‐lactide) (PDLLA) was synthesized by microwave‐irradiated ring‐opening polymerization catalyzed by stannous octoate (Sn(Oct)₂) under atmosphere. The effects of heating medium, monomer purity, catalyst concentration, microwave irradiation time, and vacuum level were discussed. Under the appropriate conditions such as carborundum (SiC) as heating‐medium, 0.15% catalyst, lactide with purity above 99.9%, 450 W microwave power, 30 min irradiation time, and atmosphere, PDLLA with a viscosity–average molecular weight (M_η) over 2.0 × 10⁵ and a yield over 85% was obtained. The dismission of vacuum to ring‐opening polymerization of D ,L ‐lactide (DLLA) under microwave irradiation simplified the process greatly. The temperature under microwave irradiation and conventional heating was compared. The largely enhanced ring‐opening polymerization rate of DLLA under microwave irradiation was the coeffect of thermal effects and microwave effects. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2244–2247, 2006     

Expeditious synthesis of novel aromatic polyamides from 5-[3-phenyl-2-(9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboximido)propanoylamino]isophthalic acid and various diamines using microwave-assisted polycondensation

A new diacid monomer, 5-[3-phenyl-2-(9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboximido)propanoylamino]isophthalic acid was successfully synthesized starting from cis-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboxylic acid anhydride and l-phenylalanine. A highly effective, very fast microwave method is described to synthesize optically active aromatic polyamides (PA)s under microwave heating for only 3 min. Generally, better yields are obtained under faster and cleaner reactions when compared to those from conventional heating. Therefore, this approach could considerably reduce the synthesis time, cost, and energy. The resulting PAs had inherent viscosities in the range of 0.35–0.58 dL/g. All of the these polymers having bulky anthracenic and amino acid functionality in the side chain showed excellent solubility and readily dissolved in various solvents such as N-methyl-2-pyrrolidinone, N,N-dimethylacetamide and N,N-dimethylformamide. PAs were thermally stable, with 10% weight loss recorded at 385 °C and 341 °C in the nitrogen atmosphere, and char yields at 800 °C higher than 50% and glass transition temperature above 180 °C.     

Microwave assisted polycondensation of polyimides by [4,4′‐(hexafluoroisopropylidene)diphthalic anhydride,pyromellitic dianhydride] and [2,4,6‐trimethyl‐m‐phenylenediamine]. Power,time, and solvent effect

The microwave assisted polycondensation of two polyimides were studied using pyromellitic dianhydride (PMDA), and 4,4′‐(hexafluoroisopropyliden)diphthalic anhydride (6FDA) as dianhydride monomers and 2,4,6‐trimethyl‐m‐phenylenediamine (TrmPD), as diamine monomer, under microwave irradiation in DMF and DMSO solvents. The structure and performance of polymers were characterized by Fourier Transform Infrared Spectroscopy (FTIR), viscosity, density, and Thermogravimetric Analysis (TGA). The results show that the polyimides can be obtained in a short reaction time with high intrinsic viscosity and high yield. The effect of the presence of a bridging group, ? C(CF₃)₂? , in the monomer structure is apparent in the permeability parameters of the macromolecules as polymer (6FDA‐TrmPD) always presents better results than polymer (PMDA‐TrmPD). Properties as density and T_g increases with the time exposition to the microwave irradiation. Polyimides obtained present good thermal properties because they began to lose weight in a range of 8–16% at high temperature as 450°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polycondensation of sodium tetrazodiphenyl naphthionate and pyromellitic dianhydride under microwave irradiation and the performance of the third‐order nonlinear optics

Sodium tetrazodiphenyl naphthionate and pyromellitic dianhydride were polycondensed under microwave irradiation and oil‐bath heating. The resultant poly(amic acid) was imidized in the solid phase by microwave irradiation and oil‐bath heating. The effects of the reaction temperature, the concentration of monomers, the monomer ratio, and the microwave irradiation time on the conversion, intrinsic viscosity, and third‐order nonlinear optical (NLO) coefficient of the polymer were investigated. The results showed that the polycondensates had high third‐order NLO coefficients (χ⁽³⁾ = 1.476 × 10^?12esu) and very fast time responses (15.79 ps). The χ⁽³⁾ values of the polycondensates under microwave irradiation were higher than those of conventional thermopolymerization. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1121–1128, 2003     

Polyamides obtained by direct polycondesation of 4‐[4‐[9‐[4‐(4‐aminophenoxy)‐3‐methyl‐phenyl] fluoren‐9‐YL]‐2‐methyl‐phenoxy]aniline with dicarboxylic acids based on a diphenyl‐silane moiety

Polyamides (PAs) containing fluorene, oxyether, and diphenyl‐silane moieties in the repeating unit were synthesized in > 85% yield by direct polycondesation between a diamine and four dicarboxylic acids. Alternatively, one PA was synthesized from an acid dichloride. The diamine 4‐[4‐[9‐[4‐(4‐aminophenoxy)‐3‐methyl‐phenyl]fluoren‐9‐yl]‐2‐methyl‐phenoxy]aniline ( 3 ) was obtained from the corresponding dinitro compound, which was synthesized by nucleophilic aromatic halogen displacement from p‐chloronitrobenzene and 9,9‐bis (4‐hydroxy‐3‐methyl‐phenyl)fluorene ( 1 ). Monomers and polymers were characterized by FTIR and ¹H, ¹³C, and ²⁹Si‐NMR spectroscopy and the results were in agreement with the proposed structures. PAs showed inherent viscosity values between 0.14 and 0.43 dL/g, indicative of low molecular weight species, probably of oligomeric nature. The glass transition temperature (T_g) values were observed in the 188–211°C range by DSC analysis. Thermal decomposition temperature (TDT_10%) values were above 400°C due to the presence of the aromatic rings in the diamine. All PAs showed good transparency in the visible region (>88% at 400 nm) due to the incorporation of the fluorene moiety. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Microwave‐assisted green approach for graft copolymerization of l‐lactic acid onto starch

Poly l ‐lactic acid grafted starch (St‐g‐PLA) copolymers were directly synthesized under microwave irradiation by using sodium hydroxide (NaOH) and stannous 2‐ethyl hexanoate acting as a catalyst, without the use of toxic solvents. The product were characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (¹³C CP/MAS NMR), X‐ray diffraction (XRD), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA‐DTG). SEM analysis indicated that microwave heating had a considerable effect on the interfacial adhesion between PLA and starch. Thermogravimetric analysis (TGA‐DTG) revealed that copolymers exhibited better thermal stability. Maximum PLA grafting was achieved with the following reaction conditions: 450W microwave power, monomer ratio of 1:5 and 0.4M of NaOH. This study demonstrates that it is possible to obtain St‐g‐PLA copolymers with better processing characteristics and smaller sizes via microwave‐assisted synthesis. The applied procedure is an interesting “green” synthesis method for the production of biodegradable materials used in a diverse range of applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42937.     

Synthesis and properties of polyamides based on 5,5′‐bis[4‐(4‐aminophenoxy)phenyl]‐hexahydro‐4,7‐methanoindan

A new diamine 5,5′‐bis[4‐(4‐aminophenoxy)phenyl]‐hexahydro‐4,7‐methanoindan ( 3 ) was prepared through the nucleophilic displacement of 5,5′‐bis(4‐hydroxylphenyl)‐hexahydro‐4,7‐methanoindan ( 1 ) with p‐halonitrobenzene in the presence of K₂CO₃ in N,N‐dimethylformamide (DMF), followed by catalytic reduction with hydrazine and Pd/C in ethanol. A series of new polyamides were synthesized by the direct polycondensation of diamine 3 with various aromatic dicarboxylic acids. The polymers were obtained in quantitative yields with inherent viscosities of 0.76–1.02 dl g⁻¹. All the polymers were soluble in aprotic dipolar solvents such as N,N‐dimethylacetamide (DMAc) and N‐methyl‐2‐pyrrolidone (NMP), and could be solution cast into transparent, flexible and tough films. The glass transition temperatures of the polyamides were in the range 245–282 °C; their 10% weight loss temperatures were above 468 °C in nitrogen and above 465 °C in air. © 2000 Society of Chemical Industry     

Synthesis,characterization and thermal degradation of poly[2‐(3‐p‐bromophenyl‐3‐methylcyclobutyl)‐2‐hydroxyethylmethacrylate]

In this work, 2‐(3‐p‐bromophenyl‐3‐methylcyclobutyl)‐2‐hydroxyethylmethacrylate (BPHEMA) [monomer] was synthesized by the addition of methacrylic acid to 1‐epoxyethyl‐3‐bromophenyl‐3‐methyl cyclobutane. The monomer and poly(BPHEMA) were characterized by FT‐IR and [¹H] and [¹³C]NMR. Average molecular weight, glass transition temperature, solubility parameter, and density of the polymer were also determined. Thermal degradation of poly[BPHEMA] was studied by thermogravimetry (TG), FT‐IR. Programmed heating was carried out at 10 °C min⁻¹ from room temperature to 500 °C. The partially degraded polymer was examined by FT‐IR spectroscopy. The degradation products were identified by using FT‐IR, [¹H] and [¹³C]NMR and GC‐MS techniques. Depolymerization is the main reaction in thermal degradation of the polymer up to about 300 °C. Percentage of the monomer in CRF (Cold Ring Fraction) was estimated at 33% in the peak area of the GC curve. Intramolecular cyclization and cyclic anhydride type structures were observed at temperatures above 300 °C. The liquid products of the degradation, formation of anhydride ring structures and mechanism of degradation are discussed. © 1999 Society of Chemical Industry