Rheo‐kinetic evaluation on the formation of urethane networks based on hydroxyl‐terminated polybutadiene

Rheo‐kinetic studies on bulk polymerization reaction between hydroxyl‐terminated polybutadiene (HTPB) and di‐isocyanates such as toluene‐di‐isocyanate (TDI), hexamethylene‐di‐isocyanate (HMDI), and isophorone‐di‐isocyanate (IPDI) were undertaken by following the buildup of viscosity of the reaction mixture during the cure reaction. Rheo‐kinetic plots were obtained by plotting ln (viscosity) vs. time. The cure reaction was found to proceed in two stages with TDI and IPDI, and in a single stage with HMDI. The rate constants for the two stages k₁ and k₂ were determined from the rheo‐kinetic plots. The rate constants in both the stages were found to increase with catalyst concentration and decrease with NCO/OH equivalent ratio (r‐value). The ratio between the rate constants, k₁/k₂ also increased with catalyst concentration and r‐value. The extent of cure reaction at the point of stage separation (x_i) increased with catalyst concentration and r‐value. Increase in temperature caused merger of stages. Arrhenus parameters for the uncatalyzed HTPB‐isocyanate reactions were evaluated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1869–1876, 2001     

Structure and properties of polyurethane acrylate prepolymers based on hydroxy‐terminated polybutadiene

Precursors of polyurethane acrylate based on hydroxy‐terminated polybutadiene (HTPB) soft segments, different diisocyanate and hydroxy ethyl acrylate (HEA) as hard units, were synthesized in bulk or in solution in methyl methacrylate. During precursor synthesis (in bulk), microphase separation was observed by small‐angle X‐ray scattering (SAXS). Diffusing particles are around 50 Å in size and are assumed to be assembling of hard segments. From these morphologies, it can be deduced that some isocyanate groups were trapped/or buried in hard domains. At a larger scale, around millimeters, hard segment crystallites were observed. Properties such as molar masses, melting and glass‐transition temperatures, and viscosities were correlated with precursor structure and morphology. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 225–233, 2002     

Fine‐tuning the mechanical properties of hydroxyl‐terminated polybutadiene/ammonium perchlorate‐based composite solid propellants by varying the NCO/OH and triol/diol ratios

Changes in the mechanical properties of hydroxyl‐terminated polybutadiene/ammonium perchlorate‐based composite solid propellants were studied during the curing period with respect to variations in the crosslink density, which was predominantly determined by the equivalent ratio of diisocyanate to total hydroxyl (NCO/OH ratio) and the equivalent ratio of triol to diol (triol/diol ratio). For this purpose, 16 propellants were prepared in different compositions through changes in the NCO/OH ratios (0.81, 0.82, 0.83, and 0.85) for each triol/diol ratio (0.07, 0.09, 0.11, and 0.13) and were tested for their mechanical properties immediately after curing. The propellants with an NCO/OH ratio of 0.82 had minimum stress, modulus, and hardness with maximum strain capability, whereas the propellants with an NCO/OH ratio of 0.85 showed just the opposite behavior. Variations in the isocyanate level seemed to have more effect on the mechanical properties at higher triol/diol ratios. It was also concluded that the propellants with triol/diol–NCO/OH combinations of 0.11–0.83, 0.11–0.85, 0.13–0.81, 0.13–0.83, and 0.13–0.85 were not acceptable for upper stage case‐bonded rocket applications because of either high tensile strength or high modulus. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2072–2079, 2002; DOI 10.1002/app.10605     

Properties and pervaporation separation of hydroxyl‐terminated polybutadiene‐based polyurethane/poly(methyl metharcylate) interpenetrating networks membranes

Hydroxyl‐terminated polybutadiene (HTPB), 4,4′‐dicyclohexyl methane diiscyanate (H₁₂MDI), and 1,4‐butane diol are used to synthesize polyurethane (PU) solutions by two‐stage process. Interpenetrating networks (IPNs) of HTPB‐based PU and poly(methyl methacrylate) (PMMA) with HTPB/MMA (wt/wt % ratio) = 2.0, 1.5, 1.0, 1.5, 0.8, and 0.6, which are designated as IPN1 to IPN5, respectively, are synthesized by sequential polymerization technique. Thermal properties, tensile strength, and contact angle of membranes increase with the increase of MMA content, while the elongation of membranes show the reverse trend. Characterization of membranes are investigated by C?C/C?O absorption ratio and infrared absorption frequency shiftment. These PU and IPN membranes are used for the separation of ethanol/water and isopropanol/water solution by pervaporation test. IPN3 membrane possesses the largest pervaporation permeability and the separation factor. The pervaporation results of ethanol/water feed has the same trend as that of isopropyl alcohol (IPA)/water solution. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Influence of hydroxyl‐terminated polybutadiene additives on the poly(ether sulfone) ultra‐filtration membranes

Hydroxyl‐terminated polybutadiene (HTPB) was blended into a poly(ether sulfone) (PES) casting solution used to prepare ultra‐filtration (UF) membranes via the phase inversion technique. The membranes were then characterized by contact angle (CA) measurements and UF experiments. The CA was increased with the addition of HTPB in the PES membrane and also by lowering the gelation bath temperature. It was observed that the CA was lower for membranes prepared with N‐methyl‐2‐pyrrolidinone (NMP) as the solvent than those using N,N‐dimethylacetamide (DMAc) as solvent. The flux values were higher for membranes made using a 4°C gelation bath when compared with the ambient temperature ((25 ± 1)°C) irrespective of the cast solvents, NMP or DMAc. The flux values were much higher and the solute separations were lower for the HTPB‐based PES membranes than for the pure PES membrane, when the membranes were cast with DMAc as a solvent. On the other hand, both flux and separation values were much lower for the HTPB‐based PES membranes than for the pure PES membrane, when the membranes were cast using NMP. Atomic force microscopy and scanning electron microscopy were used for morphological characterization and the correlation of topography/photography with the performance data was also examined. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2292–2303, 2006     

Viscoelastic behavior in a hydroxyl‐terminated polybutadiene gum and its highly filled composites: Effect of the type of filler on the relaxation processes

Investigations have been ongoing to learn the rheological and/or mechanical behavior of composite solid propellants based on hydroxyl‐terminated polybutadiene (HTPB). The mechanical properties of these materials are related to the macromolecular structure of the binder as well as to the content and nature of the fillers. The viscoelastic behavior of an HTPB binder and its composites with different types of fillers was surveyed by dynamic mechanical analysis over a wide range of temperatures. This technique has clearly demonstrated a two‐phase morphology developed in these systems. The temperature location, intensity, and apparent activation energy of the distinct relaxations are discussed. The dependency of the relaxation processes on filler content in a series of composites has elucidated the interactions between the filler particles and the existing hard‐ and soft‐segment domains within the polyurethane matrix. It was observed that the nature of the filler significantly affects the relaxation process associated with the hard‐segment domains of the polymeric structure. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1705–1712, 2003     

Effect of imide–oxazolidinone modification on the thermal and mechanical properties of HTPB‐polyurethanes

Imide‐ and oxazolidinone‐incorporated polyurethanes, based on hydroxy‐terminated polybutadiene (HTPB), were synthesized and characterized. Reaction of the blocked isocyanate terminals of the HTPB prepolymer with diepoxy compounds, containing preformed imide groups, was the strategy followed. The diepoxy resins were derived through reaction of an aliphatic and an aromatic dicarboxylic acid with preformed imide groups with a diepoxy resin. The intermediates and the polyurethane–imide–oxazolidinone were characterized by chemical, spectral, and elemental analyses. Incorporation of these heterocyclic groups caused dramatic improvements in the thermal and mechanical properties and the thermomechanical profile of the system. The improvements in properties were proportional to the hard‐segment content of the modified polyurethanes. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1731–1738, 1999     

Effects of ion group content and polyol molecular weight on physical properties of HTPB‐based waterborne poly(urethane‐urea)s

A series of waterborne poly(urethane‐urea)s, WPUUs, based on using nonpolar hydroxyl‐terminated polybutadiene (HTPB) as the soft segment, were successfully synthesized in this article. The effects of the COOH group content and soft‐segment molecular weight (Mn_s) on the dispersion, morphology, and physical properties were investigated. Variations of the particle size, viscosity, and zeta potential were first governed by the hydrophilicity of the polymer chain, and then by the swelling derived from water. Fourier transfer infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) indicated that the degree of phase separation decreased as the COOH group content increased or as Mn_s decreased. However, the hydrogen bonding between the soft and hard segments and the two‐phase mixing could not occur in this nonpolar HTPB‐based WPUU system, indicating that the hard segments tended to form smaller domains and to pack more loosely. It was attributed to the fact that the presence of bulky ionic salt groups destroyed the ordered arrangement of the hard segments. In this case, the increases of the interface area between the soft and hard phases resulted in that the present behaviors were similar to the phase mixing. In tensile properties, HTPB‐based WPUUs exhibited higher tensile stress, elongation at break, and modulus as the COOH group content decreased or as Mn_s decreased. In thermal degradation, the introduction of HTPB polyol improved the thermal stability of WPUU. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Effect of solvent exposure on the properties of hydroxy‐terminated polybutadiene‐based polyurethanes

Hydroxy‐terminated polybutadiene‐based prepolyurethanes and diamine chain extended polyurethane‐ureas were prepared and treated with various organic solvents in the moisture‐cured state in order to modify their ultimate strength. FTIR studies with solvent‐treated polyurethanes and polyurethane‐ureas confirmed that organic solvents penetrated inside the polyurethane hard segments and affected hydrogen bonding. The polar and non‐polar solvents showed different abilities to penetrate into polyurethane hard segments. Solvent treatment after moisture curing increased the tensile strength of these polyurethanes and polyurethane‐ureas with respect to control samples. The stress–strain behaviour of solvent‐treated polyurethane follows the constrained junction model. The change in hard segment crystallinity on solvent treatment has been explained by wide‐angle X‐ray diffraction study. The better orientation in polybutadiene soft segments evidenced from SEM (scanning electron microscopy) pictures is believed to be the main reason behind the improved tensile properties of solvent‐treated polyurethane samples. The effect of solvent treatment, as well as stretching, on the diffusion coefficient of hexane in polyurethanes was investigated. Copyright © 2003 Society of Chemical Industry     

Synthesis and properties of poly(amide–imide)s based on N,N′‐bis(4‐carboxyphenyl)‐4,4′‐oxydiphthalimide,p‐aminobenzoic acid and various aromatic diamines

A new diimide–diacid monomer, N,N′‐bis(4‐carboxyphenyl)‐4,4′‐oxydiphthalimide (I), was prepared by azeotropic condensation of 4,4′‐oxydiphthalic anhydride (ODPA) and p‐aminobenzoic acid (p‐ABA) at a 1:2 molar ratio in a polar solvent mixed with toluene. A series of poly(amide–imide)s (PAI, III_a–m) was synthesized from the diimide–diacid I (or I′, diacid chloride of I) and various aromatic diamines by direct polycondensation (or low temperature polycondensation) using triphenyl phosphite and pyridine as condensing agents. It was found that only III_k–m having a meta‐structure at two terminals of the diamine could afford good quality, creasable films by solution‐casting; other PAIs III using diamine with para‐linkage at terminals were insoluble and crystalline; though III_g–i contained the soluble group of the diamine moieties, their solvent‐cast films were brittle. In order to improve their to solubility and film quality, copoly(amide–imide)s (Co‐PAIs) based on I and mixtures of p‐ABA and aromatic diamines were synthesized. When on equimolar of p‐ABA (m = 1) was mixed, most of Co‐PAIs IV had improved solubility and high inherent viscosities in the range 0.9–1.5 dl g^?1; however, their films were still brittle. With m = 3, series V was obtained, and all members exhibited high toughness. The solubility, film‐forming ability, crystallinity, and thermal properties of the resultant poly(amide–imide)s were investigated. © 2002 Society of Chemical Industry     

Phase equilibrium in the diglycidyl ether of bisphenol A–hydroxyl‐terminated oligobutadiene derivatives systems

The phase equilibrium in the binary systems based on hydroxyl‐terminated butadienes and diglycidyl ether of bisphenol A has been studied in wide ranges of temperature and compositions of the solution. The analysis of the obtained experimental and calculated data shows that the molecular weight, content of hydroxyl groups, functionality of the oligomer, and the presence of bromine in the oligomer affect the level of the thermodynamic compatibility. An increase in the content of hydroxyl groups and bromine results in an increase in the compatibility of the components. The results obtained are interpreted in terms of the Flory–Huggins theory. The correlation between the phase boundary concentrations and an upper critical solution temperature and solubility parameters of the oligobutadienes has been established. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 953–957, 1999     

Mechanical and surface properties of membranes prepared from waterborne cationic hydroxyl‐terminated polydimethylsiloxane/polyurethane surfactant‐free micro‐emulsion

With the action of catalyst and cosolvent, a series of hydroxyl‐terminated polydimethylsiloxane (HPMS) based polyurethane (PU) micro‐emulsion were gotten by surfactant‐free copolymerization. They were successfully prepared by reacting isophorone isocyanate, poly(tetramethylene glycol), and HPMS with N‐methyldiethanolamine (MDEA) as chain extender and trimethylolpropane (TMP) as crosslinker. After neutralizing with dimethyl sulfate and inversing the emulsion polymerization with deionized water, a series of microemulsions were obtained. The emulsions were then cast into membranes named as PU–HPMS. The mechanical properties and water absorption of the PU–HPMS were determined and simultaneously the effects of the content of hard segment, solvent, TMP, MDEA, HPMS, and the molecular weight of soft segment were studied. It is noticed that the tensile strength decreased and elongation at break increased in the HPMS/PU when compared with pure PU, which confirm that PU was end‐capped with PDMS. It is also noticed that water absorption increased in the HPMS/PU when compared with pure PU. As HPMS content increased from 0.0 to 25.0 wt %, the surface free energies decreased from 0.3446 to 0.2317 mN/cm and water absorption decreased from 11.2% to 0.14%. The surface free energies of the membranes were decreased by more than 32.76%, which demonstrate that the membrane surfaces have excellent water and oil repellency. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 40–46, 2006     

Synthesis and properties of novel polyurethane‐urea insulating coatings from hydroxyl‐terminated prepolymers and blocked isocyanate curing agent

A novel series of one‐pack solvent borne polyurethane‐urea insulating coatings was prepared from hydroxyl‐terminated prepolymers (HTP) and blocked isocyanate curing agent (BIC). HTP was prepared from poly z(tetramethylene ether)glycol (PTMEG) with excess amount of toluene diisocyanate (TDI) and subsequent reaction of NCO‐terminated polyurethane with tris(hydroxymethyl‐aminomethane) (TRIS). BIC was prepared from the reaction of trimethylol propane, TDI, and N‐methyl aniline. HTP, BIC, and final products were characterized by conventional methods, and the curing condition was optimized via gel content measurements. Crosslink density of samples was determined via equilibrium swelling method, using Flory‐Rehner equations. Thermal, mechanical, and electrical properties as well as the chemical resistance of prepared coatings were evaluated and compared with commercially available formulations. Effects of structural parameters on physical, electrical, mechanical, and dynamic mechanical (DMTA) properties of the polyurethane‐urea coatings were investigated. The investigation of results showed superior electrical and mechanical properties of prepared green coating as a tailor‐made electrical insulator for metals. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Enhanced fracture toughness of epoxy resins with novel amine‐terminated poly(arylene ether sulfone)–carboxylic‐terminated butadiene‐acrylonitrile–poly(arylene ether sulfone) triblock copolymers

Amine‐terminated poly(arylene ether sulfone)–carboxylic‐terminated butadiene‐acrylonitrile–poly(arylene ether sulfone) (PES‐CTBN‐PES) triblock copolymers with controlled molecular weights of 15,000 (15K) or 20,000 (20K) g/mol were synthesized from amine‐terminated PES oligomer and commercial CTBN rubber (CTBN 1300x13). The copolymers were utilized to modify a diglycidyl ether of bisphenol A epoxy resin by varying the loading from 5 to 40 wt %. The epoxy resins were cured with 4,4′‐diaminodiphenylsulfone and subjected to tests for thermal properties, plane strain fracture toughness (K_IC), flexural properties, and solvent resistance measurements. The fracture surfaces were analyzed with SEM to elucidate the toughening mechanism. The properties of copolymer‐toughened epoxy resins were compared to those of samples modified by PES/CTBN blends, PES oligomer, or CTBN. The PES‐CTBN‐PES copolymer (20K) showed a K_IC of 2.33 MPa m^0.5 at 40 wt % loading while maintaining good flexural properties and chemical resistance. However, the epoxy resin modified with a CTBN/8K PES blend (2:1) exhibited lower K_IC (1.82 MPa m^0.5), lower flexural properties, and poorer thermal properties and solvent resistance compared to the 20K PES‐CTBN‐PES copolymer‐toughened samples. The high fracture toughness with the PES‐CTBN‐PES copolymer is believed to be due to the ductile fracture of the continuous PES‐rich phases, as well as the cavitation of the rubber‐rich phases. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1556–1565, 2002; DOI 10.1002/app.10390     

Investigation of acetyl ferrocene migration from hydroxyl‐terminated polybutadiene based elastomers by means of ultraviolet–visible and atomic absorption spectroscopic techniques

Migration and leakage of some mobile components in rocket propellant produces an inhomogeneous composition region at which migration takes place, which can lead to premature detonation, changes in ballistic characteristics, and so on. It is, therefore, important to be able to predict the behavior of low‐molecular‐weight mobile additives and to control the leakage of them from the propellant. At this point, our chief interest was to study the magnitude of the migration and to understand the factors that influence the migration process. In this study, the migration of a ferrocene‐based burning‐rate catalyst [acetyl ferrocene (AcF)] a from hydroxyl‐terminated polybutadiene (HTPB) based elastomer in the presence of a plasticizer (dioctyl adipate) was examined in accelerated aging conditions at 60°C for various time intervals. We also tried to minimize the migration of AcF from the loaded to the unloaded part by using an extra barrier layer consisting of polyfunctional aziridine (AST D45+) in addition to the HTPB–toluene diisocyanate composition. The migration enhanced with aging of the AcF and the barrier effects of the layer with intensified crosslink density to this migration were studied extensively. The migration was monitored by both ultraviolet–visible and atomic absorption spectroscopy (AAS) methods. A comparison of the data obtained from both of these methods was also done. The two techniques were found to be in agreement, and the Fe determinations from both methods were highly correlated, suggesting that the data were reliable, although the AAS data were found to be symmetrically somewhat higher. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1654–1661, 2005     

Characterization studies on aging properties of acetyl ferrocene containing HTPB‐based elastomers

In composite solid propellants, low‐molecular‐weight species such as burning rate catalysts, plasticizer, etc. which migrate into liner and thermal insulation layers during curing and storage invariably result in poor mechanical and ballistic properties of the propellants. In the present study, the migration of the burning rate catalyst, acetyl ferrocene, was investigated spectrophotometrically (UV–visible) by evaluating the extent of hindrance to such migration after applying a barrier (liner) of various crosslink densities between the additive (HTPB‐TDI‐plasticizer–acetyl ferrocene) and nonadditive (HTPB‐TDI) gumstocks replicating the propellant and insulating layer, respectively. Enhancing the crosslink densities of liner via a trifunctional aziridine crosslinking agent inhibited migration. The aging of additive gumstock was done at 60°C and its mechanical properties and extent of acetyl ferrocene migration were also evaluated and analyzed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2538–2545, 2006     

Synthesis of novel polyurethanes containing dioxybenzylidenecyanoacetate,as non‐linear optical chromophores and their properties

Methyl 3,4‐di‐(2′‐hydroxyethoxy)benzylidenecyanoacetate (3) was prepared by hydrolysis of methyl 3,4‐di‐(2′‐vinyloxyethoxy)benzylidenecyanoacetate (2). Diol 3 was condensed with 2,4‐toluenediisocyanate, 3,3′‐dimethoxy‐4,4′‐biphenylenediisocyanate, and 1,6‐hexamethylenediisocyanate to yield polyurethanes 4, 5 and 6 containing the non‐linear optical (NLO) chromophore 3,4‐dioxybenzylidenecyanoacetate. The resulting polyurethanes 4–6 were soluble in common organic solvents such as acetone and DMF. T_g values of the polymers obtained from DSC thermograms were in the range 80–102 °C. Polymers 4–6 showed thermal stability up to 300 °C in TGA thermograms, and electro‐optic coefficients (r₃₃) of the poled polymer films were in the range 10–12 pm V^?1 at 633 nm, which are acceptable for NLO device applications. © 2002 Society of Chemical Industry     

Preparation and properties of organo‐soluble polyimides based on 4,4′‐diamino‐3,3‐dimethyldiphenylmethane and conventional dianhydrides

4,4′‐Diamino‐3,3′‐dimethyldiphenylmethane was used to prepare polyimides in an attempt to achieve good organo‐solubility and light color. Polyimides based on this diamine and three conventional aromatic dianhydrides were prepared by solution polycondensation followed by chemical imidization. They possess good solubility in aprotonic polar organic solvents such as N‐methyl 2‐pyrrolidone, N,N‐dimethyl acetamide, and m‐cresol. Polyimide from 4,4′‐diamino‐3,3′‐dimethyldiphenylmethane and diphenylether‐3,3′,4,4′‐tetracarboxylic acid dianhydride is even soluble in common solvents such as tetrahydrofuran and chloroform. Polyimides exhibit high transmittance at wavelengths above 400 nm. The glass transition temperature of polyimide from 4,4′‐diamino‐3,3′‐dimethyldiphenylmethane and pyromellitic dianhydride is 370°C, while that from 4,4′‐diamino‐3,3′‐dimethyldiphenylmethane and diphenylether‐3,3′,4,4′‐tetracarboxylic acid dianhydride is about 260°C. The initial thermal decomposition temperatures of these polyimides are 520–540°C. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1299–1304, 1999     

Curing behavior of 4,4′‐diamonodiphenyl methane‐based benzoxazine oligomers/bisoxazoline copolymers and the properties of their cured resins

1,3‐Phenylene bisoxazoline is synthesized and characterized. The optimal synthetic conditions for yield (92%) are as follows: reaction temperature = 115°C; ratio (mol) of ethanolamine to 1,3‐dicyanobenzene = 2.5 : 1; ratio (mol) of zinc acetate to 1,3‐dicyanobenzene = 0.055; reaction time = 6 h. 4,4′‐diamonodiphenyl methane‐based benzoxazine and its oligomers (Oligo‐Da) are synthesized and characterized. The curing behavior and properties of the Oligo‐Da/1,3‐PBO copolymer resins are investigated. It was found that the cure induction time and cure time of the molten mixture from Oligo‐Da/1,3‐PBO could be reduced, compared with that from Oligo‐Ba/1,3‐PBO, especially above 175°C. The reason lies in that the bisphenol generated in ring opening of Ba has more steric hindrance than the phenol generated in ring opening of Da because of isopropyl group. Thus, the Mannich bridge structure in the Da polymer is relatively much easier to form between the ortho positions of phenolic hydroxyl groups than that in the Ba polymer. Curing temperature of Oligo‐Da/1,3‐PBO could be lowered with triphenylphosphite as a catalyst. SEM results confirm that 1,3‐PBO could toughen Oligo‐Da system when the mol ratio of 1,3‐PBO and Oligo‐Da is ≤1 because of the formation of ether–amide bonds. However, a brittle fracture surface is observed because of too higher crosslinking density of the cured resin, when the mol ratio of 1,3‐PBO and Oligo‐Da is >1. The cured resin from Oligo‐Da/1,3‐PBO has superior heat resistance, electrical insulation, and water resistance than that from Oligo‐Ba/1,3‐PBO. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1359–1366, 2006     

Synthesis and properties of TLCPs with 2,6‐naphthalene‐based mesogen,polymethylene spacer,and nonlinear 4,4′‐thiodiphenyl links

A series of new thermotropic main‐chain liquid crystalline copolyesters were prepared by polycondensation of 2,6‐naphthalenedicarbonyl chloride, 4,4′‐thiodiphenol, and α,ω‐alkanediols (n = 4–10) in diphenyl ether at 200°C. Thermal transition behaviors of these copolyesters were investigated by differential scanning calorimetry. Moreover, their thermal stabilities and mesomorphic textures were studied by thermogravimetric analysis and polarizing optical microscopy, respectively. Corresponding model compounds with terminal mesogenic units and central polymethylene spacers were also synthesized for comparison. Both copolymers and model compounds exhibit odd–even dependency of melting temperatures, transition enthalpy (ΔH_m), and entropy (ΔS_m) on the number of methylene units in the spacer. However, the odd–even effects in model compounds are much more distinctive. Nematic mesophases are the only texture observed in melts, except the model compounds with longer methylene units (n = 8, 10), in which smectic mesophases can be observed. The T_m values of the copolyesters (TDP/HD = 1/1) are between 233 and 259°C, depending on spacer length. The initial decomposition temperatures of the copolyesters are above 419°C under N₂ atmosphere. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1536–1546, 2002