Synthesis and electro‐optical properties of novel Y‐type polyurethanes containing dioxynitrostilbene

3,4‐Di‐(2′‐hydroxyethoxy)‐4′‐nitrostilbene (2) was prepared by the reaction of 2‐iodoethanol with 3,4‐dihydroxy‐4′‐nitrostilbene. Diol 2 was condensed with 2,4‐toluenediisocyanate, 3,3′‐dimethoxy‐4,4′‐biphenylenediisocyanate and 1,6‐hexamethylenediisocyanate to yield novel Y‐type polyurethanes 3–5 containing dioxynitrostilbene as a non‐linear optical (NLO)‐chromophore. Polymers 3–5 were soluble in common organic solvents, such as acetone and DMF. These polymers showed thermal stability up to 280 °C in TGA thermograms with T_g values in the range of 100–143 °C in DSC thermograms. The approximate lengths of aligned NLO‐chromophores of the polymers estimated from AFM images were around 2 nm. The SHG coefficients (d₃₃) of poled polymer films were around 4.5 × 10^?8 esu. Poled polymer films had improved temporal and long‐term thermal stability owing to the hydrogen bonding of urethane linkage and the main‐chain character of the polymer structure, which are acceptable for NLO device applications. Copyright © 2004 Society of Chemical Industry     

Synthesis of novel poly(vinyl ether)s containing the oxybenzylidenemalononitrile group as a nonlinear optical chromophore,and their electro‐optic properties

2,4‐Di‐(2′,2′‐dicyanovinyl)‐1‐(2′‐vinyloxyethoxy)benzene and 2,4‐di‐(2′‐carbomethoxy‐2′‐cyanovinyl)‐1‐(2′‐vinyloxyethoxy)benzene were prepared by condensation of 4‐(2′‐vinyloxyethoxy)isophthaldehyde with malononitrile and methyl cyanoacetate, respectively. The two vinyl monomers were polymerized with boron trifluoride etherate as a cationic initiator to yield poly(vinyl ether)s containing two oxybenzylidenemalononitrile and oxybenzylidenecyanoacetate groups, which are effective chromophores for second‐order nonlinear optical applications. These polymers were soluble in common organic solvents such as acetone and dimethyl sulforide. They showed thermal stabilities up to 300 °C from thermogravimetric analysis (TGA), with differential scanning calorimeter (DSC) thermograms giving T_g values in the range 73–87 °C. The second harmonic generation (SHG) coefficients (d₃₃) of poled polymer films were around 1.8 × 10^?9 esu, and these polymers showed good long‐term thermal stability for 60 days at room temperature, which is acceptable for nonlinear optical (NLO) device applications. Copyright © 2004 Society of Chemical Industry     

Preparation and electro‐optic properties of novel Y‐type polyimides with highly enhanced thermal stability of second harmonic generation

BACKGROUND: In the development of nonlinear optical (NLO) polymers for electro‐optic device applications, stabilization of electrically induced dipole alignment is one of the important criteria. Polyimides for NLO applications have attracted attention because of their high T_g values and high thermal stability. In this work we designed and synthesized a new type of NLO polyimide, in which the pendant NLO chromophores are parts of the polymer backbone. These mid‐type NLO polymers are expected to have the merits of both main‐chain and side‐chain NLO polymers: stabilization of dipole alignment and good solubility. RESULTS: 3,4‐Bis‐(3,4‐dicarboxyphenylcarboxyethoxy)‐4′‐nitrostilbene dianhydride was prepared and reacted with the corresponding aromatic diamine to yield unprecedented Y‐type polyimides containing 3,4‐dioxynitrostilbenyl groups as NLO chromophores, which constituted parts of the polymer backbones. The resulting polyimides are soluble in polar solvents such as dimethylformamide and dimethylsulfoxide. These polymers showed a thermal stability up to 320 °C in thermogravimetric thermograms with T_g values obtained from differential scanning calorimetry thermograms in the range 143–164 °C. The second harmonic generation (SHG) coefficients (d₃₃) of poled polymer films at the 1064 nm^?1 fundamental wavelength were around 9.45 × 10^?18 C. CONCLUSION: The dipole alignment exhibited exceptionally high thermal stability even at 30 °C higher than T_g. There was no SHG decay below 180–190 °C because of the partial main‐chain character of the polymer structure, which is acceptable for NLO device applications. Copyright © 2007 Society of Chemical Industry     

Synthesis and properties of novel poly(meth)‐acrylates containing tricyanocyclopropyl groups for piezoelectric applications

o‐(2,2,3‐Tricyano‐3‐carbomethoxycyclopropyl)phenoxyethyl acrylate ( 5a ) and o‐(2,2,3‐tricyano‐3‐carbomethoxycyclopropyl)phenoxyethyl methacrylate ( 5b ) were prepared by reactions of bromomalononitrile with methyl o‐(2‐acryloyloxyethoxy)benzylidenecyanoacetate and methyl o‐(2‐methacryloyloxyethoxy)benzylidenecyanoacetate respectively. The dipole moments of 5a and 5b , calculated by atom superposition and electron delocalization molecular orbital method, were 2.75–3.47 D. Monomers 5a and 5b were polymerized with free‐radical initiators to obtain the polymers with tricyanocyclopropane ring as a piezoelectric chromophore in the pendant group. The resulting polymers 6a and 6b were soluble in common organic solvents such as acetone and DMF. Polymers 6a and b showed thermal stability up to 280 °C in TGA thermograms. T_g values obtained from DSC thermograms were in the range 125–140 °C. Piezoelectric coefficients (d₃₁) of the poled films were 1.2–1.4 pC N^?1. These polymers showed good temporal and long‐term thermal stabilities which are acceptable for piezoelectric device applications. Copyright © 2003 Society of Chemical Industry     

Synthesis and properties of novel polyurethanes containing 2,4-dioxybenzylidenecyanoacetate group as a NLO-chromophore for electro-optic applications

Summary Methyl 2,4-bis-(2'-hydroxyethoxy)benzylidenecyanoacetate (3) was prepared by hydrolysis of methyl 2,4-bis-(2'-vinyloxyethoxy)benzylidenecyanoacetate (2). Diol 3 was condensed with 2,4-toluenediisocyanate, 3,3'-dimethoxy-4,4'-biphenylene-diisocyanate, and 1,6-hexamethylenediisocyanate to yield polyurethanes 4–6 containing the NLO-chromophore 2,4-dioxybenzylidenecyanoacetate. The resulting polyurethanes 4–6 were soluble in common organic solvents such as acetone and DMF. Polymers 4–6 showed a thermal stability up to 280°C in TGA thermograms with T _g values obtained from DSC thermograms in the range of 66–114°C. The SHG coefficients (d₃₃) of poled polymer films were around 7.8 × 10⁻⁹ esu. Received: 25 February 2002/ Revised version: 25 March 2002/ Accepted: 29 March 2002     

Synthesis and characterization of novel polyaspartimides derived from 2,2′‐dimethyl‐4,4′‐bis(4‐maleimidophenoxy)biphenyl and various diamines

A novel bismaleimide, 2,2′‐dimethyl‐4,4′‐bis(4‐maleimidophenoxy)biphenyl, containing noncoplanar 2,2′‐dimethylbiphenylene and flexible ether units in the polymer backbone was synthesized from 2,2′‐dimethyl‐4,4′‐bis(4‐aminophenoxy)biphenyl with maleic anhydride. The bismaleimide was reacted with 11 diamines using m‐cresol as a solvent and glacial acetic acid as a catalyst to produce novel polyaspartimides. Polymers were identified by elemental analysis and infrared spectroscopy, and characterized by solubility test, X‐ray diffraction, and thermal analysis (differential scanning calorimetry and thermogravimetric analysis). The inherent viscosities of the polymers varied from 0.22 to 0.48 dL g⁻¹ in concentration of 1.0 g dL⁻¹ of N,N‐dimethylformamide. All polymers are soluble in N‐methyl‐2‐pyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide, dimethylsulfoxide, pyridine, m‐cresol, and tetrahydrofuran. The polymers, except PASI‐4, had moderate glass transition temperature in the range of 188°–226°C and good thermo‐oxidative stability, losing 10% mass in the range of 375°–426°C in air and 357°–415°C in nitrogen. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 279–286, 1999     

Enhancement of nonlinear optical and thermal properties of polyurethanes by modifying the chromophores with fused heterocyclic and pyrimidine rings

This article describes the synthesis of substituted triazolo[3,4‐b]‐thiadiazole heterocycles based nonlinear optical (NLO) responsive chromophores. To enhance the NLO properties of the chromophores, the pyrimidine ring was introduced with an appropriate π‐bonding. With these chromophores, different series of polyurethanes were prepared by condensation with tolylene‐2,4‐diisocyanate and 3,3′‐dimethoxy‐4,4′‐biphenylene diisocyanate. The structure of the resulting chromophores and polyurethanes was confirmed using Fourier transform infrared, proton nuclear magnetic resonance, and Carbon Hydrogen Nitrogen (CHN) analyzer. The inherent viscosities (η_inh) of the polyurethanes measured by Ubbelohde viscometer were in the range of 0.2324–0.2760 dl/g. Thermal behavior of the polyurethanes was investigated using differential scanning calorimetry and thermogravimetric analysis. The molecular orientation in polyurethane films was induced by a corona poling, and this was ascertained using ultraviolet‐visible spectrophotometer and atomic force microscope. The thicknesses and refractive indices of thin films were determined by an Ellipsometer. Polyurethanes exhibited excellent solubility in most of the common organic solvents. The second harmonic generation (SHG) coefficients (d₃₃) of the poled polyurethanes ranged from 63.20 and 95.32 pm/V at 532 nm. None of the polyurethanes showed SHG decay below 100°C, and retained 95% of the signal even up to 500 h. The resulting enhanced NLO efficiency and longer temporal stability make these polyurethanes as promising candidates for photonic devices. POLYM. ENG. SCI., 59:500–509, 2019. © 2018 Society of Plastics Engineers     

Direct (hetero)arylation polymerization for the synthesis of donor–acceptor conjugated polymers based on N‐benzoyldithieno [3,2‐b:2′,3′‐d]pyrrole and diketopyrrolopyrrole toward organic photovoltaic cell application

In this research, new donor–acceptor (D‐A) photovoltaic polymers were synthesized from dithieno[3,2‐b:2′,3′‐d]pyrrole electron donor derivatives, including N‐benzoyldithieno[3,2‐b:2′,3′‐d]pyrrole and N‐(4‐hexylbenzoyl)dithieno[3,2‐b:2′,3′‐d]pyrrole, in combination with the electron deficient unit 2,5‐bis(2‐ethylhexyl)‐3,6‐di(thiophen‐2‐yl)‐2,5‐dihydropyrrolo[3,4‐c]pyrrole‐1,4‐dione via direct (hetero)arylation polymerization. The D‐A conjugated polymers obtained were characterized via ¹H NMR, gel permeation chromatography, Fourier transform infrared spectroscopy, DSC, XRD, photoluminescence and UV–visible methods. In addition, these D‐A polymers were used as activated layers in bilayer and bulk heterojunction structures for the fabrication of organic photovoltaic cells. © 2019 Society of Chemical Industry     

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 and characterization of novel polyurethanes containing tricyanocyclopropane ring for piezoelectric applications

Summary 1-(2',2',3'-Tricyano-3'-carbomethoxycyclopropyl)-3,4-di-2'-hydroxyethoxybenzene (4) was prepared by the reaction of bromomalononitrile with methyl 3,4-di-(2'-hydroxyethoxy)benzylidenecyanoacetate (3). Diol 4 was condensed with 3,4-toluenediisocyanate and 3,3'-dimethoxy-4,4'-biphenylenediisocynate to yield polyurethanes 5 and 6 containing multicyanocyclopropane functionalities in the pendant group. The resulting polymers 5 and 6 were soluble in common organic solvents and the inherent viscosities were in the range of 0.25–0.30 dL/g. Polyurethanes 5 and 6 showed a thermal stability up to 300°C in TGA thermograms. Solution-cast films showed T _g values in the range of 100–130°C and piezoelectric coeffcients (d₃₁) of the poled polymer films were 1.8–2.0 pC/N, which are acceptable for piezoelectric device applications. Received: 14 December 2000/Accepted: 22 January 2001     

Molecular design,synthesis, and electro‐optic properties of novel Y‐type polyesters with high thermal stability of second harmonic generation

3,4‐Di‐(2′‐hydroxyethoxy)‐4′‐nitrostilbene was prepared and condensed with terephthaloyl chloride, adipoyl chloride, and sebacoyl chloride to yield novel Y‐type polyesters containing NLO‐chromophore dioxynitrostilbenyl groups, which constituted parts of the polymer backbone. Polymers were found soluble in common organic solvents such as acetone and N,N‐dimethylformamide. They showed thermal stability up to 300 °C in thermogravimetric analysis with glass‐transition temperatures obtained from differential scanning calorimetry in the range 110–152 °C. The second harmonic generation (SHG) coefficients (d₃₃) of poled polymer films at a 1064 cm^?1 fundamental wavelength were around 3.51 × 10^?8 esu. The dipole alignment exhibited high thermal stability even at 10 °C higher than the glass‐transition temperature, and there was no SHG decay below 120 °C for one of these polymers due to the partial main‐chain character of polymer structure, which was acceptable for NLO device applications. Copyright © 2005 Society of Chemical Industry     

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 polyurethanes containing dioxynitrostilbene as a NLO-chromophore and their properties

Summary 3,4-Di-(2'-hydroxyethoxy)-4'-nitrostilbene (2) were prepared by the reaction of 2-iodoethanol with 3,4-dihydroxy-4'-nitrostilbene (1). Diol 2 was condensed with 2,4-toluenediisocyanate and 3,3'-dimethoxy-4,4'-biphenylenediisocynate to yield polyurethanes 3 and 4 containing the NLO-chromophore 3,4-dioxy-4'-nitrostilbene. Polymers 3 and 4 were soluble in common organic solvents such as acetone and DMSO. T _g value of the resulting polymers was in the range of 109–114°C. Electrooptic coefficient (r₃₃) of the poled polymer films were in the range of 20–25 pm/V at 633 nm. Polymers 3 and 4 showed a thermal stability up to 300°C in TGA thermograms, which is acceptable for NLO device applications. Received: 29 September 1999/Revised version: 19 November 1999/Accepted: 25 November 1999     

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     

Synthesis and characterization of novel benzhydrol-containing poly(amide-imide)s

A series of novel benzhydrol-containing poly(amide-imide)s (PAIs) have been prepared from a new diimide-dicarboxylic acid, N,N′-bis(4-hydroxycarbonyl)-benzhydrol-3,3′,4,4′-tetracarboxydiimide (BHTDA-DIA), with various diamines by direct polycondensation using triphenyl phosphite and pyridine as condensing agents. The polymers obtained had inherent viscosities of 0.35–0.96 dl g⁻¹. All these PAIs, except polymer PAI-2, were soluble in N-methyl-2-pyrrolidinone and N,N-dimethylacetamide containing LiCl (1 wt%). Tough and flexible PAI films could be obtained by casting PAIs from their DMAc or NMP solutions, except for polymer PAI-2. The polymer films had a tensile strength of 93–111 MPa, an elongation at break range of 4–6%, and an initial modulus range of 2.7–3.8 GPa. The glass transition temperatures of most polymers were found to be above 255 °C. These polymers were fairly stable up to a temperature around or above 400 °C, and lost 10% weight in the range 426–507 °C in nitrogen and 423–515 °C in air. © 1999 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     

Synthesis and nonlinear optical properties of a novel polyurethane containing cyanovinylthiophene with enhanced thermal stability of dipole alignment for electro‐optic applications

Stabilization of electrically induced dipole alignment is one of the important criteria in the development of nonlinear optical (NLO) polymers for electro‐optic device applications. Polyurethanes for NLO applications have attracted attention because of their high thermal stability due to hydrogen bonding. In the work reported here, we designed and synthesized a new type of NLO polyurethane, in which the pendant NLO chromophores are part of the polymer backbone. This mid‐type NLO polymer is expected to have the merits of both main‐chain and side‐chain NLO polymers, namely stable dipole alignment and good solubility. 1‐[3,4‐Di‐(2‐hydroxyethoxy)phenyl]‐2‐(2‐thienyl)ethene was prepared and condensed with 3,3′‐dimethoxy‐4,4′‐biphenylenediisocyanate to yield a polyurethane. This polyurethane was reacted with tetracyanoethylene to give a novel Y‐type polyurethane (7) containing 1‐(3,4‐dioxyphenyl)‐2‐[5‐(1,2,2‐tricyanovinyl)‐2‐thienyl]ethenes as NLO chromophores, which constitute part of the polymer backbone. Polyurethane 7 is soluble in common organic solvents such as N,N‐dimethylformamide and dimethylsulfoxide. It shows a thermal stability up to 280 °C from thermogravimetric analysis with a glass transition temperature obtained from differential scanning calorimetry of ca 162 °C. The second harmonic generation (SHG) coefficient (d₃₃) of a poled polymer film of he polyurethane at 1560 nm fundamental wavelength is ca 1.11 × 10^?18 C. Polymer 7 exhibits an enhanced thermal stability and no significant SHG decay is observed below 150 °C, which is acceptable for NLO device applications. Copyright © 2009 Society of Chemical Industry     

Synthesis and nonlinear optical properties of novel y‐type polyurethanes containing different concentrations of chromophore

A new series of Y‐type polyurethanes containing different concentrations of nonlinear optical (NLO) chromophore with aniline donor and tricyanofurane (TCF) acceptor have been successfully prepared, and characterized by FTIR, UV‐Vis, and ¹H‐NMR spectra. New polyurethanes were synthesized with different chromophore contents by introducing diol N, N‐dihydroxyethylaniline or 4‐[N, N‐(dihydroxyethyl)amino]benzaldehyde. These NLO polyurethanes exhibit good film forming property and high thermal stability up to 281°C. The highest electro‐optic coefficient (r₃₃) of polymers is up to 39 pm V^?1 measured by simple reflection technique at 1310 nm, and the temporal stability of the poling‐induced order at elevated temperature of 80°C was much improved through the introducing of hydrogen bonding interaction in this system. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Crystallography and Structure–Property Relationships of 2,2″,4,4′,4″,6,6′,6″‐Octanitro‐1,1′ : 3′,1″‐Terphenyl (ONT)

An X‐ray crystallographic study of 2,2″,4,4′,4″,6,6′,6″‐octanitro‐1,1′ : 3′,1″‐terphenyl (ONT) has been carried out. The dihedral angles between benzene rings vary from 84.9° to 89.4°. Nonbinding interatomic distances of oxygen atoms inside all the nitro groups are shorter than the intermolecular contact radii for oxygen. On the basis of the DFT B3LYP/6‐31(d, p) method it was found that the difference between the X‐ray structure in the solid phase and DFT result for the gas phase is 98 kJ mol⁻¹, and the bearer of the highest initiation reactivity of the ONT molecule in the solid phase should be the nitro group at 4″‐position, in contrast to those at 4′‐ or 6′‐position that play this role in the isolated molecule. It has been stated that the nitro groups at the reaction centers of the ONT molecule are relatively well specified by their ¹⁵N NMR chemical shifts.     

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