Synthesis and characterization of copolyesters of PET and substituted p-hydroxybenzoic acids

Random copolyesters of different compositions were synthesized by melt polycondensation of poly(ethylene terephthalate) and 3-bromo - and 3,5-dibromo-p-hydroxybenzoic acids. The copolymer compositions were determined by proton nuclear magnetic resonance spectroscopy. The thermal behavior of these copolyesters was investigated by differential scanning calorimetry. The glass transition temperature, crystallization temperature, and decomposition temperature were found to increase with increase in the paraoxybenzoate content of the copolyesters. The limiting viscosity number and the weight-average molecular weight were determined.     

Liquid crystal polymers. I. Preparation and properties of p-hydroxybenzoic acid copolyesters

High molecular weight copolyesters were prepared by the acidolysis of poly(ethylene terephthalate) with p-acetoxybenzoic acid and polycondensation through the acetate and carboxyl groups. The mechanical properties of the injection-molded copolyesters containing 40–90 mole- % p-hydroxybenzoic acid (PHB) were highly anisotropic and dependent upon the PHB content, polyester molecular weight, injection-molding temperature, and specimen thickness. As the injection-molding temperature increased and the specimen thickness decreased, the tensile strength, stiffness, and Izod impact strength increased when measured along the direction of flow of the polymer melt, and the coefficient of thermal expansion was zero. In some compositions these properties were superior to those of commercial glass fiber reinforced polyesters. Maximum tensile strengths, flexural moduli, notched Izod impact strengths, and minimum melt viscosities were obtained with polyesters containing 60–70 mole-% PHB. Higher oxygen indicies (39-40) and heat deflection temperatures (150-220°C) were obtained with 80–90 mole-% PHB.     

Liquid crystal polymers. I. Preparation and properties of p-hydroxybenzoic acid copolyesters

High molecular weight copolyesters were prepared by the acidolysis of poly(ethylene terephthalate) with p-acetoxybenzoic acid and polycondensation through the acetate and carboxyl groups. The mechanical properties of the injection-molded copolyesters containing 40–90 mole-% p-hydroxybenzoic acid (PHB) were highly anisotropic and dependent upon the PHB content, polyester molecular weight, injection-molding temperature, and specimen thickness. As the injection-molding temperature increased and the specimen thickness decreased, the tensile strength, stiffness, and Izod impact strength increased when measured along the direction of flow of the polymer melt, and the coefficient of thermal expansion was zero. In some compositions these properties were superior to those of commercial glass fiber reinforced polyesters. Maximum tensile strengths, flexural moduli, notched Izod impact strengths, and minimum melt viscosities were obtained with polyesters containing 60–70 mole-% PHB. Higher oxygen indicies (39–40) and heat deflection temperatures (150–220°C) were obtained with 80–90 mole-% PHB.     

Esters of 1,4-dihydropyridine-3- and -3,5-carbothiolic acids

Methods for the preparation of esters of 1,4-dihydropyridine-3- and -3,5-carbothiolic acids were developed, and their structure and reactivity were studied. A comparative analysis was made of the spectroscopic characteristics of sulfur-containing esters of the 1,4-dihydropyridine series and their oxygen analogs. More strongly expressed electron-acceptor properties of the COSAlk groupings as compared with alkoxycarbonyl substituents were observed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 219–228, February, 1982.     

Sequentially ordered,thermotropic aromatic copolyesters: Synthesis and comparison of their properties with random copolyesters

Synthetic methods of aromatic copolyesters having ordered comonomer sequence are described. In order to obtain a regular sequence copolyester, one first has to prepare a dimeric or trimeric compound with a predesigned sequence via a multistep route and then polycondense it with another difunctional compound. Low reaction temperature is required to avoid the occurrence of undesired interchange reactions that would lead to randomization of the comonomer sequence. Sequentially ordered copolyesters exhibit significant differences in thermal transitions, crystalline properties, and occasionally even in liquid crystallinity when compared with the properties of the corresponding random copolyesters. According to the preliminary results randomization in comonomer sequence of sequentially regular aromatic copolyesters above their melting points is rather rapid.     

Side chain liquid crystalline elastomers II. Thermal properties and orientational behaviour of the LCE based on unsaturated copolyesters

The effect of crosslinking density on the phase behaviour of smectic liquid crystalline networks was studied; the results showed that crosslinking in their smectic phases can greatly enhance the stability of the liquid crystalline phase. The higher the crosslinking density, the higher the smectic-isotropic transition temperature. The mechanically-induced orientation was studied by polarized FTIR spectroscopy. The smectic liquid crystalline network could be oriented parallel to the mechanical field at higher draw ratio λ, while at lower λ the mesogenic groups are oriented perpendicular to the field for the networks with higher crosslinking density. The observed mechanically-induced orientation is interpreted by a proposed mechanism.     

Thermal and pyrolysis studies of copolyesters

Random copolyesters of dimethyl terephthalate (DMT), ethylene glycol (EG), and butane-1,4-diol (BD) and the homopolyesters poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT) have been subjected to degradation and pyrolysis studies. Differential thermal analysis (DTA) showed that the decomposition temperature is dependent on the percentage of EG and BD present in the copolyesters. Thermal volatilization analysis (TVA) also showed that the decomposition temperature is dependent on the percentage of EG and BD present in the copolyesters. The trend for the decomposition temperatures obtained from TVA studies for these copolyesters is similar to such other thermal properties as melting temperature T_m, ΔH_f, ΔH_c, etc. The subambient thermal volatilization analysis (SATVA) curves obtained for these polymers are also presented. The SATVA curve is the fingerprint of the total volatile products formed during the degradation in high vacuum. The isothermal pyrolysis of these materials was carried out in high vacuum at 450°C. The products formed were separated in a gas chromatograph and were subsequently identified in a mass spectrometer. The major pyrolysis products from PBT were butadiene and tetrahydrofuran, whereas those from PET were ethylene and acetaldehyde. The ratio of acetaldehyde to ethylene increases with the EG content in the copolyester, suggesting a different decomposition mechanism compared to the decomposition mechanism of PBT and PET.     

Thermal and mechanical properties of short-segment block copolyesters and copolyether–esters

The effects of chain structure and processing variables on the microstructure and linear viscoelastic behavior of a series of copolyether–ester block polymers are described. In addition, the random copolyester analogs of the hard block are examined. The ester segments are composed of two isomers, poly(tetramethylene terephthalate) (PTMT) and poly(tetramethylene isophthalate) (PTMI), which possess significantly different crystallization kinetics. The ratio of PTMT to PTMI in the series has been systematically varied to alter the crystallizability without changing the chemical composition. The results of differential scanning calorimetry, wide-angle x-ray diffraction, and dynamic mechanical characterization are presented. Copolymerization of a second ester shortens the average sequence length of the first ester, resulting in melting-point depression for crystals of the first polyester and substantial lowering of the dynamic mechanical storage modulus above the glass transition of the intercrystalline phase. The melting-point depression may be predicted by using Flory's model for random copolymers, but the calculated heats of fusion are significantly lower than those obtained from diluent melting-point depression.     

Gas transport properties of thermotropic liquid-crystalline copolyesters. II. The effects of copolymer composition

Gas transport properties are reported for a series of compression-molded films prepared from copolyesters of hydroxybenzoic acid (HBA) and 2,6 hydroxynaphthoic acid (HNA) having 30/70, 58/42, 73/27, 75/25, and 80/20 mol % HBA/HNA. The mesomorphic and crystalline morphology of the materials was characterized using dynamic mechanical thermal analysis (DMTA), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and X-ray diffraction As evidenced by DMTA, the phenyl and naphthyl moieties of the HBA/HNA materials exhibit a significant degree of segmental mobility below the glass transition temperature. The nonlinear nature of the naphthyl unit leads to a more hindered rotation about the chain axis. Permeability measurements were made for He, H₂, O₂, N₂, Ar, and CO₂ at 35°C and the diffusivities were computed from time-lag data. As previously observed in these materials, the films exhibited excellent barrier properties resulting largely from very low gas solubility coefficients. The liquid-crystalline copolyester: (LCP) materials with the highest HNA content exhibit the best barrier properties. It appears that the more hindered motions of the naphthyl unit restrict penetrant mobility. The reduction in permeability with increased naphthyl unit content is accompanied by a very dramatic increase in selectivity between gas pairs. Fractional free volume analysis was used to correlate the transport properties of the LCP materials and other conventional polymers. A “two-phase” modification of the free volume correlation suggests that transport may likely occur in a small volume fraction of a less dense boundary phase.     

Complexes of cobalt(II), nickel(II) and copper(II) with the benzenedicarboxylic acids. Thermal properties

The thermal properties of the complexes of phthalic, isophthalic and terephthalic acid with cobalt(II), nickel(II) and copper(II) are determined by thermogravimetry (TG), differential thermogravimetry (DTG) and differential scanning calorimetry (DSC).The thermal stability of the anhydrous compounds gives, for the metal ions, a sequence Co > Ni > Cu.The thermal stability series as a function of the ligand for each metal is terephthalate > isophthalate > phthalate.     

Thermal,spectral and magnetic properties of 3,5-dimethoxybenzoates of Co(II), Ni(II) and Cu(II)

The complexes of 3,5-dimethoxybenzoates of Co(II), Ni(II) and Cu(II) have been synthesized as hydrated polycrystalline solids and characterized by elemental analysis, IR, FIR and electronic spectroscopy, magnetic studies and X-ray diffraction measurements. They possess colours typical of the M(II) ions: Cu-blue, Ni-green, Co-pink. The carboxylate groups bind as monodentate or a symmetrical, bidentate chelating or bridging ligands. The thermal stabilities were determined in air. When heated they dehydrate to form anhydrous salts which are decomposed to the oxides of respective metals. The magnetic susceptibilities of the complexes were measured over the range 77-300 K and the magnetic moments were calculated. The results reveal the complexes of Ni(II) and Co(II) to be high-spin complexes and that of Cu(II) to form dimer.     

Novel copolyesters based on poly(alkylene dicarboxylate)s: 1. Thermal behavior and biodegradation of aliphatic-aromatic random copolymers

In order to improve the thermal and mechanical properties of the poly(butylene 1,12-dodecanedioate), some novel aliphatic-aromatic random copolyesters have been prepared by starting from 1,4-butanediol and different molar ratio of 1,12-dodecanedioc acid and terephthalic acid. The samples were characterized by ¹H NMR and the molecular structure was correlated with the crystalline phase present, the level of crystallinity, the glass transition temperature, the mechanical behavior, and the biodegradability. In particular, the copolymer containing the 70 mol% of PBT repeating units notably improves the thermal and mechanical properties of the poly(butylene 1,12-dodecanedioate) towards those of PBT and maintains a very high thermal stability, but loses the biodegradability of the poly(alkylene dicarboxylate). Therefore, for this class of aliphatic-aromatic copolymers the chemical composition must be carefully chosen to reach a compromise between good thermal and mechanical performances and biodegradability, according to the necessity.     

3-硝基胍-6-(3,5-二甲基吡唑)-1,2,4,5-四嗪的晶体结构及热行为

合成了3-硝基胍-6-(3,5-二甲基吡唑)-1,2,4,5-四嗪(NDT),在二甲基甲酰胺(DMF)中培养出NDT的单晶(NDT·DMF),该晶体属于三斜晶系,P-1空间群,晶胞参数为a=0.7070(4) nm,b=0.8468(6) nm,c=1.4123(9) nm,α=73.281(8)°,β=80.423(11)°,γ=81.740(9)°,Z=2。 利用DSC和TG-DTG研究了NDT的热分解行为,其放热过程的表观活化能和指前因子分别为288.245 kJ/mol和10^29.04 s^-1。 对NDT的热安全性进行了研究,获得NDT的自加速分解温度T_SADT为212.19 ℃,热点火温度T_be为213.52 ℃,热爆炸临界温度T_bp为214.95 ℃,绝热至爆时间范围在5.43~6.26 s。     

Butylene copolyesters based on aldaric and terephthalic acids. Synthesis and characterization

The synthesis, characterization, and some properties of new copolyesters analogous to poly(butylene terephthalate) (PBT), based on L ‐arabinaric and galactaric acids, are described. These copolyesters were obtained by polycondensation reaction in the melt of mixtures of methyl 2,3,4‐tri‐O‐methyl‐L ‐arabinarate or methyl 2,3,4,5‐tetra‐O‐methyl‐galactarate and dimethyl terephthalate with 1,4‐butanediol. Their weight‐average molecular weights ranged between 10,000 and 34,000, with polydispersities ranging from 1.4 to 2.2. The composition of all the copolymers was analyzed by NMR, and was found to have a statistical microstructure. All these copolyesters were thermally stable, with degradation temperatures well above 300 °C. The melting temperature and crystallinity decreased in both series, and the glass transition temperature increased and decreased respectively, for the PBTGa and PBTAr series with increasing amounts of aldaric units in the copolyester chain. Only PBT‐derived copolyesters containing a maximum of 30% aldaric units showed discrete scattering characteristic of crystalline material. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1168–1177, 2009     

Thermochemical properties of benzoic acid derivatives X. Enthalpies of combustion and formation of 2,3-, 2,4-, 2,6-, 3,4-, and 3,5-dimethoxybenzoic acids

The energies of combustion of 2,3-, 2,4-, 2,6-, 3,4-, and 3,5-dimethoxybenzoic acids have been determined by static-bomb calorimetry. The enthalpies of formation in the crystalline state at 298.15 K have been derived for these five acids. The values obtained are:

     

	$\text{?ΔH}{}_{\mathrm{f}}{}^{\mathrm{o}}\text{(c)/kJ mol}{}^{\mathrm{?1}}$
2,3-dimethoxybenzoic acid	687.0 ± 1.4
2,4-dimethoxybenzoic acid	712.2 ± 1.4
2,6-dimethoxybenzoic acid	693.8 ± 1.4
3,4-dimethoxybenzoic acid	714.0 ± 1.4
3,5-dimethoxybenzoic acid	724.0 ± 1.5