Molecular simulation of thermophysical properties of aromatic polymers containing oxetane ring in the main chain

Molecular simulation techniques have been applied to newly synthesized aromatic polymers, containing oxetane rings in the main chain, to characterize the shape of rod‐like macromolecules. Single chains and periodic unit cells of a series of aromatic polymers with degree of polymerization 15 were used in the simulations, in accordance with the experimentally obtained one. The total potential energy was minimized and then NVE and NPT molecular dynamics simulations were performed for 1,000 ps at 11 temperatures between 10 and 1,000 K. The coefficient of asymmetry was calculated from the computer‐generated structures. The predictive capability of the NPT molecular dynamics simulation and Polymer Properties modules of Cerius² were used to estimate the orientational properties (order parameter), glass transition temperature, cohesive energy, and decomposition temperature of the polymers simulated. In general, there is a good‐to‐excellent agreement between simulated results and available experimental data of the above investigated properties. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2334–2352, 1999     

Synthesis and characterization of aromatic polyamides containing S-triazine rings in the main chain

Ten new aromatic polyamides containing s-triazine rings in the main chain were synthesized by the low temperature interfacial polycondensation technique involving the reactions of each of the two s-triazine containing diacylchlorides, viz., 2,4-bis (4-chlorocarbonylphenoxy)-6-methoxy-s-triazine and 2,4-bis(3-chlorocarbonylphenoxy)-6-methoxy-s-triazine, with five aromatic diamines namely, 4,4′-bis(4-aminophenoxy)diphenyl sulfone, 4,4′-bis(3-aminophenoxy)diphenyl sulfone, 2,2-bis[4(4-aminophenoxy) phenyl] propane, 1,4 bis (4-amino-phenoxy) benzene, and 1,3-bis (4-aminophenoxy)benzene. The resulting polyamides were characterized by viscosity measurements, IR and ¹H-NMR spectroscopy, solubility tests, x-ray diffraction, and thermogravimetry. The polyamides had inherent viscosities in the range of 0.16–1.06 dL/g in N,N-dimethylacetamide at 30°C. Most of the s-triazine containing polyamides dissolved readily at room temperature in polar solvents. Except for the polyamide PA-2, the polyamides did not lose weight below 350°C under a nitrogen atmosphere. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1077–1085, 1997     

Phase Transfer Catalysis in Polycondensation Processes: XVIII. Thermal properties and molecular simulation of some polyethers containing oxetane rings in the main chain

A study was made of the influence of the chemical structure of the chains on the thermal stability of a series of copolyethers obtained from 3,3-bis(chloromethyl)oxetane and various bisphenols: 4,4'-dihydroxyazobenzene, 4,4'-dihydroxydiphenyl, 4,4'-thiodiphenol, 1,1-bis(4-hydroxy-phenyl)ethane and 4,4'-dihydroxydiphenylsulfone. For a better correlation between chemical structure and thermal stability, molecular simulations were performed, using the HYPERCHEM (version 4.5) program. The lowest thermal stability was exhibited by the polymers that contain azobenzene units. The best thermal stability was that of the polyethers containing thiodiphenyl and 1,1-bis(phenyl)ethane units.This revised version was published online in November 2005 with corrections to the Cover Date.     

Preparation and properties of new wholly aromatic polyesters containing a terphenyl analogue of 1,3,4-thiadiazole in the main chain

Novel wholly aromatic polyesters 8 containing a terphenyl analogue of 1,3,4-thiadiazole (2,5-diphenyl-1,3,4-thiadiazole) in the main chain were synthesized by high-temperature solution polycondensation of a diacyl chloride derivative of 2,5-diphenyl-1,3,4-thiadiazole 6 with four hydroquinones 7 in 1-chloronaphthalene. These polymers 8 are insoluble in most organic solvents and decompose very rapidly above 400°C in air without showing thermotropic liquid crystalline melts.     

Liquid crystalline polymers: molecular simulation of some polyethers containing oxetanic rings in the main chain

This paper presents a conformational analysis of some polyethers containing the oxetanic ring in the main chain. The studied polymers were synthesized by phase transfer catalysis, using 3,3-bis(chloromethyl)-oxetane and various bisphenols. The analysis was performed using the Cerius² program (version 2.0) molecular simulation software for material science, designed by Molecular Simulations Incorporated (MSI). This study tries to elucidate some aspects concerning the difficulties appearing in the liquid crystalline property's characterization. These difficulties are induced by the cross-linking processes that take place in certain situations due to the opening of the oxetanic rings at high temperature.     

Linear polyesters containing isocyanurate rings

Two series of linear polyesters containing isocyanurate rings have been prepared to determine the effect of structural variations on thermal and solubility properties. The polyesters were prepared by the polycondensation reaction of isocyanurate containing difunctional acid and ester monomers with linear diols. The substituent on the isocyanurate ring and the length of the acid side chain have been shown to have considerable effect on the glass transition temperature T_g. Different solubility properties were observed for the series of polyesters in which the pendant substituent was ? C₆H₅ and the acid side-chain was ? CH₂CO₂H. These polymers were insoluble in THF, and the polyester prepared from 1,6-hexanediol was also insoluble in chloroform. Thermal gravimetric analysis (TGA) indicated that structural differences had no significant effect on the thermal stability of these linear polyesters.     

Synthesis and characterization of polyamides containing s-triazine rings in the main chain

Polyamides were synthesized from diacids containing a s-triazine ring and two aromatic diamines, namely 4,4′-diaminodiphenyl ether (ODA) and 4,4′-diaminodiphenylmethane (MDA), by direct polycondensation using the phosphorylation reaction. Polymers thus obtained were characterized by viscosity measurement, IR spectroscopy, thermogravimetry, X-ray diffraction, and solubility tests. These polyamides had inherent viscosities in the range of 0.51–0.77 dL/g, and were amorphous in nature. All the polymers were readily soluble in various organic solvents and did not lose weight below 270°C in air.     

Synthesis and properties of polyurethanes containing s-triazine rings in the main chain

Eight new diisocyanate monomers containing s-triazine ring have been prepared from the parent diacids via the Curtius rearrangement of the corresponding diacyl azides. The parent diacids were synthesised by the reaction of p- and m-hydroxybenzoic acid with 6-methoxy-2,4-dichloro-s-triazine, 6-phenoxy-2,4-dichloro-s-triazine, 6-phenyl-2,4-dichloro-s-triazine, and 2-diphenylamino-4,6-dichloro-s-triazine respectively. Polyurethanes have been synthesised by solution polymerization of these diisocyanates with ethylene glycol in N,N-dimethylacetamide (DMAC). The resulting polymers were characterized by IR spectroscopy, viscosity measurement, solubility tests, and softening points.     

Synthesis and properties of thermotropic liquid-crystalline polyesters containing 9,10-diphenylanthracene moiety in the main chain

We synthesized thermotropic liquid-crystalline polyesters in which 9,10-diphenylanthracene moieties are incorporated into the main chain type of polyester forming the chiral smectic C (Sm C*). The polymers were prepared by the isopropyltitanate-catalyzed reaction of biphenyldicarboxylic acid and the corresponding diols, with different ratios of diol of 9,10-diphenylanthracene moiety to the alkane diols (1, 5, and 10 mol %) under nitrogen atmosphere. The polymers exhibited thermotropic liquid crystals despite the presence of a bulky diphenylanthracene moiety in the main chain. The circular dichroism spectra revealed that a Sm C* phase was formed in the polymer with 1 mol % of anthracene moiety, although only an Sm A phase was formed in the other polymers. This is the first example of a Sm C* polyester containing a diphenylanthracene moiety in the main chain. Furthermore, we measured the optical properties of the polymers and found that they exhibited very high fluorescent efficiency. The fluorescence spectra of the thin film differed from that of a CH₂Cl₂ solution.     

Synthesis and characterization of new unsaturated polyesters and copolyesters containing azo groups in the main chain

A new interesting class of linear unsaturated polyesters based on dibenzylidenecycloalkanones have been synthesized by interfacial polycondensation of 4,4^′-azodibenzoyl chloride or 3,3^′-azodibenzoyl chloride with: 2,5-bis(p-hydroxybenzylidene)cyclopentanone I, 2,6-bis(p-hydroxybenzylidene)cyclohexanone II, 2,6-divanillylidenecyclohexanone III, or 2,7-bis(p-hydroxybenzylidene)cycloheptanone IV at ambient temperature. The copolyesters are also synthesized from the monomers I, II, III or IV with the diacid chlorides. The resulting polyesters and their copolyesters were characterized by elemental analyses, IR spectroscopy and solubility. Additionally, inherent viscosity of the polyesters in the range 0.32-0.86 dL g⁻¹ and the inherent viscosity of the copolyesters in the range 0.28-0.65 dL g⁻¹ were determined. The UV-visible spectra of certain polymers were measured in m-cresol solution and showed a characteristic absorption band at 435-473 nm due to n-π^* transition. The thermal properties of the polymers were evaluated by thermo gravimetric analysis and differential scanning calorimetry measurements and correlated with their structural units. The crystallinity of some polyesters and copolyesters were tested. In addition, the electrical properties of all polyesters and copolyesters were measured.     

Synthesis of polyesters containing acetylenic bonds in the chain

Summary By joint oxidative dehydropolycondensation of p-diethynylbenzene and dipropargyl esters, polymers have been obtained that contain triple bonds alternating with ester groups.     

Investigations on aromatic polyesters with polynaphthalene systems in the main chain. I. Low-temperature solution polycondensation

A series of aromatic polyesters has been prepared by low-temperature solution polycondensation of derivatives of dihydroxydinaphthyl or dihydroxydinaphthylmethane with terephthaloyl chloride. The chemical, physical, and thermal properties of some polyesters have been investigated. Some of the polyesters obtained have high melting temperatures (340–420°C) and very good thermal resistance. In spite of their high melting temperatures some polymers give solutions in organic solvents which make it possible to produce films and coatings with good dielectric and mechanical properties and with a relatively high thermal resistance.     

Investigations of aromatic polyesters with polynaphthalene systems in the main chain—VI: NMR studies of the structure of the aromatic copolyesters

Nuclear magnetic resonance spectra of several kinds of terephthalic copolyesters of 4,4′dihydroxydinaphthyl 1,1′ and 2,2 bis(4-hydroxyphenyl) propane were recorded. Proton signals of the terephthalic acid unit corresponding to heterolinkages and homolinkages could be observed in the range from 8.23 to 8.53 ppm. The average sequence lengths and the degrees of randomness in the copolyesters were calculated from the intensities of these signals.     

Investigations of aromatic polyesters with polynaphthalene systems in the main chain—VIII. Influence of the chain structure of aromatic copolyesters on their dielectric β-relaxation

A relationship has been established between the chain structure of aromatic copolyesters with polynaphthalene rings in the main chain and dielectric β-relaxation. The relationship is valid between +20° and ?180° and over the frequency range 10³Hz–10⁵Hz.     

Investigations on aromatic polyesters with polynaphthalene systems in the main chain—IX. Influence of the chain structure of aromatic copolyesters on their glass transition temperatures

Glass transition temperatures of terephthalic copolyesters of 4,4′dihydroxydinaphthyl 1,1′ and 2,2 bis(4-hydroxyphenyl)propane with various mole ratios of the comonomers and different chain structures have been measured. A relationship has been found between T_g and the chain structure of aromatic copolyesters with polynaphthalene rings in the chain.     

Thermotropic main chain liquid crystalline polyesters containing ferrocene and phosphate units: synthesis and characterization

A new series of liquid crystalline main chain copolyesters were prepared, having ferrocene in the mesogenic segment and a methyl phosphate group along with a methylene spacer. The even numbered methylene groups were varied from two to ten. Liquid crystalline behaviour was investigated on a hot stage optical polarized microscope. Thermal properties of the polymers were analysed by TGA and DSC, revealing that the polymers yield high char products, probably caused by the formation of phosphorus and iron oxides. The glass transition (T_g) temperatures of the polymers were found to be fairly low, the result of the incorporation of bulky phosphorus and ferrocene moieties in the chain. The phase behaviour was analysed and correlated with the structure of the polymers. The liquid crystalline textures of the polymers became more transparent with increasing spacer length. Energy minimized structures for the polymer repeating units reveal that both the ferrocene and phosphorus moieties produce more molecular entanglement, thus reducing the T_g and T_m of the polymers.     

Photoreactive main chain liquid crystalline polyesters containing oxadiazole and bis(benzylidene) cycloalkanone units

Photoreactive main chain liquid crystalline polyesters containing oxadiazole and bis(benzylidene)cycloalkanone moieties were synthesized and characterized by structural, thermal, mesomorphic, and optical measurements. The bis(benzylidene) cycloalkanone chromophores in the main chain can constitute both as a mesogen and photoreactive center, whereas 1,3,4‐oxadiazole is a well‐known fluorophore. The thermal properties of polymers were found to be inversely proportional not only to the spacer length but also to ring‐size of cycloalkanones. Hot stage polarized optical microscopic investigations displayed enantiotropic nematic liquid crystalline phases and development of grainy to schlieren textures depends on the length of flexible spacer in the polymer backbone which was in accordance with DSC analysis. Both photoisomerization and photodimerization are observed from the absorption spectra and discussed. The fluorescence spectra in solution state at various concentrations showed that the polymers show blue‐emission maxima and the Stokes shifts being 48–49 nm. The energy transfer occurred when increasing the concentration of the solution. The band gap energies calculated from the absorption spectra are in the range of 3.17–3.41 eV. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5760–5775, 2008