Compatibilization of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)–poly(lactic acid) blends with diisocyanates

Poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) was blended with poly(lactic acid) (PLA) with various reactive processing agents to decrease its brittleness and enhance its processability. Three diisocyanates, namely, hexamethylene diisocyanate, poly(hexamethylene diisocyanate), and 1,4‐phenylene diisocyanate, were used as compatibilizing agents. The morphology, thermomechanical properties, and rheological behavior were investigated with scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry, tensile testing, dynamomechanical thermal analysis in torsion mode (dynamic mechanical analysis), and oscillatory rheometry with a parallel‐plate setup. The presence of the diisocyanates resulted in an enhanced polymer blend compatibility; this led to an improvement in the overall mechanical performance but did not affect the thermal stability of the system. A slight reduction in the PHBV crystallinity was observed with the incorporation of the diisocyanates. The addition of diisocyanates to the PHBV–PLA blend resulted in a notable increase in the final complex viscosity at low frequencies when compared with the same system without compatibilizers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44806.     

Synthesis and characterization of new polyamides containing p‐phenylenediacryloyl moieties in the main chain

Six new polyamides 8a–f containing p‐phenylenediacryloyl moieties in the main chain were prepared by the direct polycondensation reaction of bis(p‐amidobenzoic acid)‐p‐phenylene diacrylic acid 6 with 1,4‐diphenylene diamine 7a , 1,3‐diamino toluene 7b , 1,5‐diamino naphthalene 7c , 4,4′‐diamino diphenyl ether 7d , 4,4′‐diamino diphenyl sulfone 7e , and 3,3′‐diamino diphenylsulfone 7f by using thionyl chloride, N‐methyl‐2‐pyrolidone, and pyridine as condensing agents. These new polymers 8a–f were obtained in high yield and inherent viscosity between 0.35–0.65 dL/g. The resulting polyamides were characterized by elemental analysis, viscosity measurements, thermal gravimetric analysis (TGA and DTG), solubility test, FTIR and UV–vis spectroscopy. Diacid acid 6 as a new monomer containing p‐phenylenediacryloyl moiety was synthesized by using a three‐step reaction. First, p‐phenylenediacrylic acid 3 was prepared by reaction of terephthal aldehyde 1 with malonic acid 2 in the presence of pyridine, then diacid 3 was converted to p‐phenylenediacryloyl chloride 4 by reaction with thionyl chloride. Finally, bis(p‐amidobenzoic acid)‐p‐phenylene diacrylic acid 6 was prepared by the condensation reaction of phenylenediacryloyl chloride 4 with p‐aminobenzoic acid 5 . © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and luminescence properties of new blue‐light‐emitting polyconjugated poly{1,1′‐biphenyl‐4,4′‐diyl‐[1‐(4‐t‐butylphenyl)]vinylene} polymers and copolymers

Three new soluble polyconjugated polymers, all of which emitted blue light in photoluminescence and electroluminescence, were synthesized, and their luminescence properties were studied. The polymers were poly{1,1′‐biphenyl‐4,4′‐diyl‐[1‐(4‐t‐butylphenyl)]vinylene}, poly((9,9‐dioctylfluorene‐2,7‐diyl)‐alt‐{1,4‐phenylene‐[1‐(4‐t‐butylphenyl)vinylene‐1,4‐phenylene]}) [P(DOF‐PVP)], and poly([N‐(2‐ethyl) hexylcarbazole‐3,6‐diyl]‐alt‐{1,4‐phenylene‐[1‐(4‐t‐butylphenyl)]vinylene‐1,4‐phenylene}). The last two polymers had alternating sequences of the two structural units. Among the three polymers, P(DOF‐PVP) performed best in the light‐emitting diode devices of indium–tin oxide/poly(ethylenedioxythiophene) doped with poly(styrene sulfonate) (30 nm)/polymer (150 nm)/Li:Al (100 nm). This might have been correlated with the balance in and magnitude of the mobility of the charge carriers, that is, positive holes and electrons, and also the electronic structure, that is, highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels, of the polymers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 307–317, 2006     

Photodegradation mechanism and stabilization of polyphenylene oxide and rigid‐rod polymers

Poly(2,4‐dimethyl‐1,4‐phenylene oxide) (PPO), poly(benzo[1,2‐d:5,4‐d′]bisoxazole‐2,6‐diyl‐1,4‐phenylene) (PBO) and poly(benzo[1,2‐d:4,5‐d′]bisthiazole‐2,6‐diyl‐1,4‐phenylene) (PBZT), which are polymers with extended conjugated structures, undergo a self‐sensitized photo‐induced electron‐transfer reaction. A second component is not required. This article presents many similar observations on these polymers when they are exposed to light and evidence to support the proposed photo‐induced electron‐transfer mechanism. Methods to stabilize these polymers against photo‐oxidation are also described. Workers investigating other conjugated polymeric systems may find the experimental methods, observations and polymer stabilization approaches discussed in this review useful. Copyright © 2005 Society of Chemical Industry     

Energetic Material/Polymer Interaction Studied by Atomic Force Microscopy

The interactions of energetic materials and polymers have important implications in safety, long‐term storage, and performance of explosives and explosive mixtures. Atomic force microscopy was used to investigate adhesion forces at the molecular scale of nine energetic materials, organic explosives and energetic salts, on eleven common polymers (polyethylene, polyvinylalcohol, poly(vinyl chloride), polycarbonate, polystyrene, poly(methyl methacrylate), styrene‐butadiene rubber, poly(4‐vinyl phenol), poly(2,6‐dimethylphenylene oxide), poly(2,6‐diphenyl‐p‐phenylene oxide) (Tenax®), and polytetrafluoroethylene (Teflon®)). Teflon was the least adhesive polymer to all energetic materials, while no distinct trend could be elucidated among the other polymers or energetic materials.     

Synthesis of α,ω‐isocyanate telechelic polymethacrylate soft segments with activated ester side functionalities and their use for polyurethane synthesis

The synthetic route for the preparation of α,ω‐isocyanate‐telechelic poly(methyl methacrylate‐co‐acryloxysuccinimide) and α,ω‐ isocyanate‐telechelic poly(methyl methacrylate‐co‐acrylamidohexanoic succinimide) soft segments is presented. The strategy includes reversible addition fragmentation chain transfer (RAFT) copolymerization and two post polymerization modification steps. The RAFT polymerizations result in copolymers with an activated ester proportion within the polymer chains of 8% N‐acryloxysuccinimide and 5% 6‐acrylamidohexanoic succinimide. The reactivity ratios of the monomer pairs were determined. In a first post polymerization reaction carboxylic acid homo telechelic polymers were prepared by reacting the ω‐dithiobenzoate end‐group with an excess of azobis(cyanovaleric acid). In a second modification step the α‐ and ω‐carboxylic acid end‐groups were reacted with hexamethylene diisocyanate and 100% isocyanate telechelic copolymers were obtained. Finally segmented polyurethanes were prepared by coupling hexamethylene diisocyanate (HDI) end capped soft segments with hard segments composed of 1,4‐butanediol and HDI. © 2013 Society of Chemical Industry     

Synthesis and Characterization of New Diisocyanate-Based Polyurethane Cationomers

New diisocyanates, which contain tertiary nitrogen, have been prepared and used in the preparation of polyurethane cationomers. The ionomers were synthesized from commercial diisocyanates (toluene diisocyanate or hexamethylene diisocyanate) as well as from new diisocyanates [N,N′-bis(m- or p-isocyanato-phenyl)pyromellitic diimide] with polypropylene glycol, chain extended with 1,4-butanediol and/or N-methyldiethanolamine and then quaternized with 1,4-bis(chloromethyl)benzene. The cationomers thus formed were characterized by thermogravimetric analysis and differential scanning calorimetric measurements.     

Properties of segmented polyurethanes derived from different diisocyanates

Various segmented polyurethane materials with a polyurethane hard segment (HS) content of 40 wt % were prepared by bulk polymerization of a poly(tetramethylene ether) glycol with M_n of 2000, 1,4‐butanediol, and various diisocyanates. The diisocyanates used were pure 4,4′‐diphenylmethane diisocyanate (MDI), 2,4‐toluene diisocyanate (T100), toluene diisocyanate containing 80% 2,4‐isomer and 20% 2,6‐isomer (T80), isophorone diisocyanate (IPDI), hydrogenated 4,4′‐diphenylmethane diisocyanate (HMDI), and 1,6‐hexane diisocyanate (HDI). The segmented polyurethane materials were characterized by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), tensile properties, tear strength, and Shore A hardness. The DSC and DMA data show that the thermal transitions are influenced significantly by the diisocyanate structure. In the segmented polyurethane materials with aliphatic HS, the polyether soft segment (SS) is immiscible with the HS. However, in the segmented polyurethane materials with aromatic HS, the SS is partially miscible with the HS. The diisocyanate structure also influences the mechanical properties significantly and is described as the effect of symmetry and chemical structure of the HS. Various solution polymerized polyurethane resins with solid content of 30 wt % were also prepared and their thickness retention, water resistance, and yellowing resistance were determined for the evaluation of their usage as wet process polyurethane leather. The polyurethane resin with aliphatic HS show poorer thickness retention but better yellowing resistance. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 167–174, 2000     

Improvement of thermal stability of new heteroaromatic poly(azomethine urethane)s

New poly(azomethine urethane)s were synthesized in the conventional literature manner by reacting a new bisphenol‐containing azomethine group, N,N′‐bis(4‐hydroxyl‐3‐methoxy benzylidine)‐2,6‐diaminopyridine (I) with various diisocyanates, such as hexamethylene diisocyanate (HDI) (a), methylene‐4,4′‐diphenyl diisocyanate (MDI) (b), and toluene‐2,4‐diisocyanate (TDI) (c). The resulting polymers I(a–c) were confirmed by ¹H‐NMR, FTIR, UV, and CHN analyses. Thermogravimetric analysis (TGA) revealed that the polymers have high thermal stability. A semicrystalline behavior was noticed for polymers by wide‐angle X‐ray diffraction (WAXD) and differential scanning calorimetry (DSC). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1198–1204, 2006     

Structure–property relationship of blocked diisocyanates: synthesis of polyimides using imidazole‐blocked isocyanates

Imidazole, 2‐methylimidazole and benzimidazole‐blocked aromatic and aliphatic diisocyanates have been prepared and polymerized with pyromellitic dianhydride in the presence of a basic catalyst. The polymers are characterized with FTIR, ¹H NMR and ¹³C NMR spectroscopy and GPC, DSC and TGA. The structure–property relationship of blocked diisocyanates are discussed in terms of molecular weight of the polyimides obtained. Considering the blocking agent, GPC results show that the benzimidazole blocked adduct yields higher molecular weight polymer than the 2‐methylimidazole‐blocked adduct which, in turn, yields higher molecular weight polymer than the imidazole‐blocked adduct. Considering the structure of the isocyanate, the molecular weight of polymer increases from isophorone diisocyanate to hexamethylene diisocyanate and to toluene diisocyanate (TDI). DSC traces of the polymers derived from TDI show glass transitions (T_g) in the temperature range 152–180 °C and the values increase from the polymer based on imidazole‐blocked TDI to 2‐methylimidazole‐blocked TDI and to benzimidazole‐blocked TDI. © 2000 Society of Chemical Industry     

Electroluminescence and photovoltaic properties of poly(p‐phenylene vinylene) derivatives with dendritic pendants

A copolymer of dendronized poly(p‐phenylene vinylene) (PPV), poly{2‐[3′,5′‐bis (2′‐ethylhexyloxy) bnenzyloxy]‐1,4‐phenylene vinylene}‐co‐poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylene vinylene] (BE‐co‐MEH–PPV), was synthesized with the Gilch route to improve the electroluminescence and photovoltaic properties of the dendronized PPV homopolymer. The polymer was characterized by ultraviolet–visible absorption spectroscopy, photoluminescence spectroscopy, and electrochemical cyclic voltammetry and compared with the homopolymers poly{2‐[3′, 5′‐bis(2‐ethylhexyloxy) benzyloxy‐1,4‐phenylene vinylene} (BE–PPV) and poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylenevinylene] (MEH–PPV). Polymer light‐emitting diodes based on the polymers with the configuration of indium tin oxide (ITO)/poly(3,4‐ethylene dioxythiophene) : poly(styrene sulfonate) (PEDOT : PSS)/polymer/Ca/Al were fabricated. The electroluminescence efficiency of BE‐co‐MEH–PPV reached 1.64 cd/A, which was much higher than that of BE–PPV (0.68 cd/A) and a little higher than that of MEH–PPV (1.59 cd/A). Photovoltaic properties of the polymer were studied with the device configuration of ITO/PEDOT : PSS/polymer : [6,6J‐phenyl‐C₆₁‐butyric acid methyl ester] (PCBM)/Mg/Al. The power conversion efficiency of the device based on the blend of BE‐co‐MEH–PPV and PCBM with a weight ratio of 1 : 3 reached 1.41% under the illumination of air mass 1.5 (AM1.5) (80 mW/cm²), and this was an improvement in comparison with 0.24% for BE–PPV and 1.32% for MEH–PPV under the same experimental conditions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

A comparison of triazole cross‐linked polymers based on poly‐AMMO and GAP: Mechanical properties and curing kinetics

Triazole cross‐linked polymers based on poly(3‐azidomethyl‐3‐methyl oxetane) (poly‐AMMO) and glycidyl azide polymer (GAP) were prepared using bis‐propargyl‐1,4‐cyclohexyl‐dicarboxylate (BPHA) as curing agent, respectively. Swelling tests demonstrated that cross‐linking densities of the resulted polymers both increased with the increase of BPHA. Triazole cross‐linked polymers based on poly‐AMMO showed superior tensile strength and elongation at break than those of GAP at comparable stoichiometry. The curing kinetics was also investigated by FTIR, and GAP exhibited faster reaction rate when reacted with BPHA than that of poly‐AMMO. In addition, with the increase of cross‐linking density, the glass transition temperature (T_g) of as‐prepared polymers significantly increased, and poly‐AMMO‐based polymers showed stronger T_g‐raising effect than GAP‐based polymers. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43341.     

Synthesis and characterization of novel optically active poly(imide–urethane)s derived from N,N′‐(pyromellitoyl)‐bis‐(L‐leucine) diisocyanate and aromatic diols

N,N′‐(Pyromellitoyl)‐bis‐(L ‐leucine) diacid was reacted with ethyl chloroformate in the presence of triethylamine followed by reaction with activated sodium azide and gave N,N′‐(pyromellitoyl)‐bis‐(L ‐leucine) diacylazide in high yield. This diacylazide was heated in dry benzene and gave the unstable N,N′‐(pyromellitoyl)‐bis‐(L ‐leucine) diisocyanate ( 5 ) in quantitative yield. Thus, diisocyanate 5 was generated in situ and polycondensation reaction of this monomer with several aromatic diols, such as 4,4′‐dihydroxybiphenyl, 1,4‐hydroquinone, bisphenol A, phenolphthalein and 1,4‐dihydroxyanthraquinone, was performed in dry toluene under refluxing in the presence of 1,4‐diazabicyclo[2.2.2]octane (triethylenediamine) as a catalyst. The polymerization reactions proceeded within 48 h, producing a series of optically active poly(imide–urethane)s with good yield and moderate inherent viscosity in the range 0.18–0.28 dl g^?1. All of the above polymers were fully characterized by infrared spectra, elemental analyses and specific rotation. Some structural characterization and physical properties of these optically active poly(imide–urethane)s are reported Copyright © 2003 Society of Chemical Industry     

Preparation of poly(1,4‐cyclohexylenedimethylene phthalate)s and their use as modifiers for aromatic diamine‐cured epoxy resin

Poly(1,4‐cyclohexylenedimethylene phthalate) s, prepared by the reaction of phthalic anhydride and 1,4‐cyclohexane dimethanol (35/65 or 73/27 mol % cis/trans or trans alone), have been used to improve the toughness of bisphenol‐A diglycidyl ether epoxy resin cured with 4,4′‐diaminodiphenyl sulfone. The aromatic polyesters include poly(cis/trans‐1,4‐cyclohexylenedimethylene phthalate) (PCP) based on a commercial cyclohexanedimethanol, poly(trans‐1,4‐cyclohexylenedimethylene phthalate) (trans‐PCP) and poly(cis/trans‐1,4‐cyclohexylenedimethylene phthalate) (cis‐rich PCP) prepared from a cis‐rich diol. The polyesters used were soluble in the epoxy resin without solvents and were effective as modifiers for toughening the cured epoxy resin. For example, the inclusion of 20 wt% of PCP (MW 6400 g mol⁻¹) led to an 80% increase in the fracture toughness (K_IC) of the cured resin with no loss of mechanical and thermal properties. The toughening mechanism is discussed in terms of morphological and dynamic viscoelastic behaviours of the modified epoxy resin system. © 2000 Society of Chemical Industry     

Molecular mobility and hydration properties of segmented polyurethanes with varying structure of soft‐ and hard‐chain segments

The molecular mobility and hydration properties of model segmented polyurethanes from either poly(propylene glycol) (PPG) or poly(butylene adipate) (PBAD), both of molecular weight 2000 (soft segments), and three different diisocyanates (all‐trans 4,4′‐dicyclohexylmethane diisocyanate, 100% t,t HMDI; HMDI with 20% of trans isomers, 20% t,t HMDI; and 4,4′‐diphenylmethane diisocyanate, MDI) (hard segments) were investigated using differential scanning calorimetry (DSC), thermally stimulated depolarization currents (TSDC) measurements, ac dielectric relaxation spectroscopy (ac DRS), equilibrium water‐sorption isotherms (ESI), and dynamic water‐sorption isotherms (DSI). No effects of the structure and of the amount of the soft segments on the overall degree of microphase separation (DMS) into microphases rich in soft and hard segments, respectively, were observed. On the contrary, DMS depends on the composition of the diisocyanates used and systematically increases in the order MDI, 20% t,t HMDI, 100% t,t HMDI as indicated by DSC, TSDC, and ac DRS. The PPG‐based polyurethanes are characterized by larger values of water content at saturation, h, and smaller values of the diffusion coefficient of water, D. h increases with temperature, indicating that the sorption process is endothermic. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1209–1221, 1999     

Preparation and biodegradation of hydroxyl terminated poly(fumaric acid‐co‐diethylene glycol) and its segmented polyurethane

Hydroxyl terminated poly(fumaric acid‐co‐diethylene glycol), poly(FA‐co‐DEG) was prepared by melt polycondensation. The resultant unsaturated aliphatic polyester was characterized by Fourier transform infrared (FTIR) spectroscopy, hydroxyl value, acid value, and intrinsic viscosity. Its enzymatic degradation and crosslinking behavior as well as the effect of crosslinking degree on enzymatic degradation were also investigated. The crosslinking degree and reduction of carbon–carbon double bonds revealed excellent self‐crosslinking nature of poly(FA‐co‐DEG) at high temperature. The results of enzymatic degradation showed that poly(FA‐co‐DEG) has excellent biodegradability and that the biodegradation can be controlled by the crosslinking degree. Polyurethane was prepared by the reaction of poly(FA‐co‐DEG), 2,4‐toluene diisocyanate (TDI), and 1,4‐butanediol (BD). It was found that the biodegradation of the obtained polyurethane was slower than that of the original unsaturated aliphatic polyester poly(FA‐co‐DEG). The peeling strength of the polyurethane was very high, supporting better adhesion property with enhanced crosslinking. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Probing effects of alternately‐embedded phenoxy phenyl lateral groups on properties of novel aromatic poly(ether‐urea)s

A new class of alternate aromatic poly(ether‐urea)s having bulky phenoxy phenyl lateral groups was prepared by the reaction of 2,2′‐bis[(p‐phenoxy phenyl)]‐4,4′‐diaminodiphenyl ether (PPAPE) with two diisocyanates, isophorone diisocyanate and 2,4‐tolylene diisocyanate. The limited viscosity values as well as M _n and M _w values of the resulting polymers were determined. The resulting poly(ether‐urea)s could be easily cast into optically‐transparent, flexible, and light color films. The cut‐off wavelength values and the percentage of transmittance at 800 nm were found to be at about 415 nm and 85%, respectively. PPAPE‐derived poly(ether‐urea)s showed a low‐crystallinity and had excellent solubility in polar organic solvents. T_onset, T_g, T_d5%, and T_d10% values of the PPAPE‐derived polymers measured from their DSC and TGA thermograms were up to 270, 280, 315, and 340°C, respectively. Surface morphology of the resulted poly(ether‐urea)s were also evaluated by their scanning electron microscopy images. Excellent organo‐solubility, satisfactory film quality, moderate T_g values, and good thermal stability make this class of poly (ether‐urea)s promising high‐performance polymeric materials. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of 1,4‐cyclohexylene units on thermal properties of poly(1,4‐cyclohexylenedimethylene adipate) and similar aliphatic polyesters

In the field of aliphatic polyesters there is a great interest in building novel macromolecular structures that may effectively feature the required properties for specific applications. For this reason, it is extremely important to understand the correlations between chemical structure and final performance. Monomers based on the 1,4‐cyclohexylene unit are interesting as they are potentially bio‐based and rigid enough to improve glass transition and melting temperatures. The present paper describes the preparation of samples of poly(1,4‐cyclohexylenedimethylene adipate), characterized by different cis/trans isomeric ratio of the cyclic units, the analysis of their thermal properties and the comparison with the properties of similar polymers such as poly(butylene adipate), poly(butylene‐1,4‐cyclohexanedicarboxylate) and poly(1,4‐cyclohexylenedimethylene‐1,4‐cyclohexanedicarboxylate). The effect of the rigidity and of the stereochemistry of the 1,4‐cyclohexylene unit on the thermal properties was analysed. Such an effect reaches its maximum level when the cyclic‐containing monomers are the diacid or the diester and when the trans isomers predominate. Starting from such a result, the combination of specific cyclic building blocks with the correct cis/trans ratio makes it possible to build macromolecular structures with the required final properties.     

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     

Thermally stable polyureas and poly(urea‐imide)s containing zinc and nickel napthtrien complexes

Two new napthtrien metal complexes, MNapth₂trien; where M = Zn and Ni, were synthesized and used for the synthesis of metal‐containing polyureas and poly(urea‐imide)s. MNapth₂trien underwent polymerization reaction with two diisocyanates, namely, 4,4′‐diphenylmethane diisocyanate and isophorone diisocyanate to yield polyureas. Poly(urea‐imide)s were obtained by the synthesis of metal‐containing isocyanate‐terminated polyurea prepolymers from the reaction between MNapth₂trien and excess diisocyanates, which could then undergo further reaction with different dianhydrides. The dianhydrides used were pyromellitic dianhydride and benzophenone‐3,3′,4,4′‐tetracarboxylic dianhydride. The polymers were characterized by infrared, nuclear magnetic resonance, elemental analysis, X‐ray diffraction, solubility, and viscosity. Glass transition temperature of the polymers was obtained from differential scanning calorimetry and dynamic mechanical thermal analysis. Thermal stability of polymers was studied by thermogravimetric analysis in air. It was found that the resulting metal‐containing polymers exhibited good thermal stability. Initial decomposition temperatures of the polymers depend on the amount of MNapth₂trien in the polymer composition. Char yields of metal‐containing poly(urea‐imide)s are higher than those of metal‐containing polyureas. Most metal‐containing polymers show good solubility in organic solvents. Shore D hardness test indicates that metal‐containing poly(urea‐imide)s are hard materials. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009