Thermotropic copolyesters having ordered comonomer sequences and flexible spacers

A series of new copolyesters having ordered comonomer sequences were synthesized via multistep routes and their properties such as glass transition (T_g) and melting temperatures (T_m), crystallization tendency, and mesomorphic properties were compared with those of the corresponding random copolyesters. All of the present copolyesters contain 1,8-octamethylene or 1,10-decamethylene spacers and hydroquinone (HQ) and terephthalic acid (TPA) moieties. In general, both melting and clearing temperatures of the ordered sequence copolyesters were much higher than those of the random counterparts. Crystallization tendency, however, was comparable. All of the present copolyesters are thermotropic and form nematic phase in melts. © 1993 John Wiley & Sons, Inc.     

Synthesis and characterization of functional aliphatic copolyesters

Functional aliphatic copolyesters of succinic acid (SA) and citric acid (CA) were synthesized via direct copolycondensation in the presence of 1,4‐butanediol, with titanium(IV) butoxide as a catalyst. The effects of the comonomer and comonomer ratio on the polycondensation and the melting and glass‐transition temperatures were investigated. The melting temperature was very sensitive to the molar ratio of the SA–CA comonomer units. The chain extension of this poly(butylene succinate citrate) was carried out with hexamethylene diisocyanate. The intrinsic viscosity, crystallinity percentage, and rheological properties of these copolyesters were also studied. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3232–3239, 2002     

Development of amorphous copolyesters based on 1,4‐cyclohexanedimethanol

The modification of poly(ethylene terephthalate) with 1,4‐cyclohexanedimethanol and the modification of poly(1,4‐cyclohexylenedimethylene terephthalate) with ethylene glycol or isophthalic acid retard the crystallization of the copolyester backbone, and over a wide range of comonomer concentrations, very slowly crystallizing, essentially amorphous copolyesters are formed. These amorphous copolyesters possess attractive physical properties such as toughness, low color, and chemical resistance, and since their first commercial introduction in 1977, these copolyesters have become the basis of a large and growing plastics business for Eastman Chemical Co. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5847–5852, 2004     

Thermotropic behavior of aromatic copolyesters based on 3,4′-substituted diphenyl ether

Recently, flexible rod-like monomers based on conformational isomerism have been used to synthesize fully aromatic thermotropic polymers of reduced processing temperature and good thermal stability. 3,4′-Dihydroxy and 3,4′-dicarboxydiphenyl ethers HE and DE, obtained by modified Ullmann condensations between proper hydroxy and bromo derivatives, are investigated as basic components for homo- and copolyesters with the above-mentioned characteristics. Homopolymers from HE and terephthaloyl chloride or DE chloride and 2-methyl (or phenyl) hydroquinone, synthesized by low temperature solution polycondensation, melt to an isotropic fluid; the chain packing is frustrated in the latter by asymmetrical substitution on the aromatic rings, which causes a sequence randomization as well as an increased chain separation. The incorporation of linear rigid units, by partial substitution of the flexible monomers with 1,4 aromatic moieties, leads to thermotropicity, but the critical content of 1,4 units varies with the steric hindrance of the diphenol. Variation of chain rigidity, arising from the chemical structure, composition and sequence distribution, can account for the thermal behavior of the samples and, in particular, for their different abilities to give liquid crystalline behavior.     

SYNTHESIS AND CHARACTERIZATION OF AROMATIC LIQUID CRYSTALLINE COPOLYESTERS WITH REGULAR SEQUENCE STRUCTURE

Several novel aromatic liquid crystalline copolyesters with regular sequence structure were prepared by melt Sehotten-Baumann polycondensation via complex monomer. Polarizing microscope with hot stage, thermal analysis and X-ray diffraction were used to investigate the structure and properties of the copolyesters. The effects of structural units, such as flexible spacer, noncolinear meta-linked phenylene unit, crankshaft unit, kink with flexible bridging unit and various substituted benzene rings on melting temperature of aromatic copolyesters were studied and discussed on the basis of crystalline structure of the polymers.     

Synthesis,characterization, and enzymatic degradation of network aliphatic copolyesters

Network copolyesters were prepared from glycerol (Yg) and sebacic acid (10) with 10–90 mol % of either succinic acid (4), 1,12-dodecanedicarboxylic acid (14), 1,18-octadecanedicarboxylic acid (20), or terephthalic acid (T). Prepolymers prepared by melt-polycondensation were cast from dimethylformamide solution and postpolymerized at 230–250°C for various periods of time to form a network. The resultant films were transparent, flexible, and insoluble in organic solvents. The network copolyesters obtained were characterized by infrared absorption spectra, wide angle X-ray diffraction analysis, density measurement, thermomechanical analysis, differential scanning calorimetry, and tensile test. The enzymatic degradation was estimated by weight loss of the network copolyester films in a buffer solution with Rhizopus delemar lipase at 37°C. The weight loss due to the enzymatic degradation was decreased with increasing comonomer content, and the copolyesters with Yg4, Yg20 and YgT more than 50 mol % were not degraded by lipase enzyme at all. On the contrary, Yg-10/14 films were degraded appreciably over whole range of comonomer composition. With increasing comonomer content, the heat distortion temperature increased gradually, while the tensile strength and Young's modulus were not changed much. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2005–2011, 1999     

Structure and temperature behavior of thermotropic liquid-crystalline Ultrax copolyesters

Phase and relaxational transitions in the commercial thermotropic liquid-crystalline copolyesters Ultrax 4002 and Ultrax 4003 were studied by X-ray diffraction, differential scanning calorimetry, and mechanical analysis. In spite of only a slight difference in the compositions of the copolyesters, considerable differences in their structure and temperature behavior were observed. In particular, it was shown that the degree of crystallinity differs by more than a factor of 2 for the as-spun fibers upon annealing above the glass-transition temperature. The type of crystalline structure as well as the ability to crystallize are also different. The glass-transition temperature of both copolyesters is determined as the temperature of the appearance of mobility of the most rigid comonomer units and does not depend on the composition of the materials. Annealed copolyesters are semicrystalline materials with a two-phase structure, where the crystalline phase coexists with a liquid-crystalline one. The structure of the latter is characterized by aperiodic positions of smecticlike layers in space. On heating the materials the crystalline phase is transformed into a pseudohexagonal mesophase indicating features of a second-order phase transition. Received: 20 July 1999 Accepted: 20 August 2000     

Effects of comonomer sequential structure on thermal and crystallization behaviors of biodegradable poly(butylene succinate‐co‐butylene terephthalate)s

In this work, new investigations on the effect of comonomer sequential structure on the thermal and crystallization behaviors and biodegradability have been implemented for the biodegradable poly(butylene succinate‐co‐butylene terephthalate) (PBST) as well as aliphatic poly(butylene succinate) (PBS). At first, these copolyesters were efficiently synthesized from dimethyl succinate and/or dimethyl terephthalate and 1,4‐butanediol via condensation polymerization in bulk. Subsequently, their molecular weights and macromolecular chain structures were analyzed by gel permeation chromatography (GPC) and nuclear magnetic resonance (NMR) spectroscopy. By means of differential scanning calorimeter (DSC) and wide‐angle X‐ray diffractometer (WAXD), thermal and crystallization behaviors of these synthesized aromatic–aliphatic copolyesters were further explored. It was demonstrated that the synthesized copolyesters were revealed to have random comonomer sequential structures with thermal and crystallization properties strongly depending on their comonomer molar compositions, and that crystal lattice structures of the new crystallizable copolyesters shifted from the monoclinic crystal of semicrystalline PBS to triclinic lattice of the poly(butylene terephthalate) (PBT) with increasing the terephthalate comonomer composition, and the minor comonomer components were suggested to be trapped in the crystallizable component domains as defects. In addition, the enzymatic degradability was also characterized for the copolyesters film samples. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1635–1644, 2006     

Axial correlation lengths for aromatic copolyesters

X‐ray methods were used to investigate the structure of Vectra® and Xydar® polyesters. Xydar® is based on the aromatic polyester prepared from p‐hydroxybenzoic acid (HBA), terephthalic acid, and biphenol. Vectra® consists of HBA and 2‐hydroxy‐6‐naphthoic acid. X‐ray fiber diagrams of these materials consist of a series of nonperiodic layer lines, which are consistent with a structure consisting of parallel chains of a random comonomer sequence. The meridional peak positions are predicted accurately for fully extended, infinite chains, and the observed and calculated intensities are also in reasonably good agreement. However, there is a less adequate match between the observed and calculated peak profiles, which are predicted to be much sharper than those observed. The latter agreement is improved with a model consisting of finite chain segments with a slightly nonlinear (sinuous) conformation. The best agreement for the observed peak profiles is obtained with an ordered segment length of 90 ± 6 Å and a sinuosity of g = 3.67 ± 0.08% for Vectra® fibers and with an ordered segment length of 104 ± 6 Å and a sinuosity of g = 3.33 ±0.08% for Xydar® fibers. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1839–1847, 2001     

Aliphatic–aromatic copolyesters derived from 2,2,4,4‐tetramethyl‐1,3‐cyclobutanediol

With the massive changes taking place in the world today, the development of new thermally and mechanically stable polymeric materials is of utmost importance. This article focuses on the synthesis and thermal characterization of a new series of copolyesters that incorporate both aromatic as well as aliphatic diols. This is of interest because most polymer materials that exhibit high thermal and/or mechanical properties contain aromatic monomer units only. These aromatic units usually contribute to either the thermal or mechanical properties but typically not both. An example of this is bisphenol A polycarbonate, which has high mechanical properties but only moderate thermal properties when compared, for example, to polyimides. In recent years there has been an interest in copolyesters that contain 2,2,4,4‐tetramethyl‐1,3‐cyclobutanediol (CBDO). This aliphatic monomer imparts some very unique thermal as well as mechanical properties. This article will report the thermal properties of a new series of CBDO‐based copolyesters. These polymers include CBDO, a series of bisphenols, and terephthaloyl chloride. The series of bisphenols discussed here include bisphenol A, AF, F, and HPF. These polymers display glass transition temperatures near 200 °C and decomposition temperatures from 390–420 °C (Argon) and from 385–410 °C (Air). © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3473–3478, 2004     

Synthesis and structure of biodegradable hexylene terephthalate-co-lactide copolyesters

To obtain a biodegradable polymer material with satisfactory thermal properties, higher elongation and modulus of elasticity, a new copolyester, poly(hexylene terephthalate-co-lactide) (PHTL), was synthesized via direct polycondensation from terephthaloyl dichloride, 1,6-hexanediol and oligo(lactic acid). The resulting copolyesters were characterized by proton nuclear magnetic resonance (¹H NMR), differential scanning calorimetry (DSC), thermogravimetry (TG) and wide-angle X-ray scattering (WAXS). By using the relative integral areas of the dyad peaks in ¹H NMR spectrum of copolyesters PHTL, the sequence lengths of the hexylene terephthalate and lactide units in the resultant copolyesters are 3.5 and 1.5, respectively. Compared to poly(hexylene terephthalate) (PHT), PHTL has lower T _m but higher T _g due to the incorporation of lactide unit into the main chains of copolyesters. The degradation test of copolyesters under a physiological condition shows that the degradability of PHTL is sped up due to incorporation of lactide segments.     

Thermotropic copolyesters of a series of aromatic diols with phenylterephthalic acid and 4,4′-oxybisbenzoic acid

Wholly aromatic, liquid crystalline, main chain copolyesters derived from various linearly substituted aromatic diols with mixtures of 2-phenylterephthalic acid and a nonlinear aromatic dicarboxylic acid, 4,4′-oxybisbenzoic acid, were prepared by acidolysis condensation polymerization reactions and characterized for their liquid crystalline properties. The formation of a liquid crystalline phase at elevated temperatures was not prevented by the introduction of up to 50 mol % of the nonlinear diacid in the copolymers, and all of those copolyesters exhibited nematic liquid crystalline phases. Furthermore, the inclusion of a nonlinear monomer was not as effective as was the presence of a phenyl substituent in decreasing the melting transition of these copolymers. All of the copolymers had high glass transition temperatures and high thermal stabilities. © 1993 John Wiley & Sons, Inc.     

Biodegradable aliphatic/aromatic copolyesters based on terephthalic acid and poly(L-lactic acid): Synthesis, characterization and hydrolytic degradation

<正>Biodegradable aliphatic/aromatic copolyesters,poly(butylene terephthalate-co-lactate)(PBTL) were prepared via direct melt polycondensation of terephthalic acid(TPA),1,4-butanediol(BDO) and poly(L-lactic acid) oligomer(OLLA). The effects of polymerization time and temperature,as well as aliphatic/aromatic moiety ratio on the physical and thermal properties were investigated.The largest molecular weight of the copolyesters was up to 64100 with molecular weight distribution index of 2.09 when the polycondensation was carried out at 230℃for 6 h.DSC,XRD,DMA and TGA analysis clearly indicated that the degree of crystallinity,glass-transition temperature,melting point,decomposition temperature, tensile strength,elongation and Young's modulus were influenced by the ratio between TPA and OLLA in the final copolyesters.Hydrolytic degradation results demonstrated that the incorporation of biodegradable lactate moieties into the aromatic polyester could efficiently improve hydrolytic degradability of the copolymer even though it still had many aromatic units in the main chains.     

Sequence distribution in polyethylene/tetramethylene terephthalate copolyesters by 13C-NMR

¹³C-NMR gives sequence information in copolyesters synthesized from ethylene glycol (EG), 1,4-butane diol (BD), and methyl terephthalate (TP). The EG-TP-EG and BD-TP-BD blocks are distinguishable from the unsymmetrical diester sequence EG-TP-BD. The carbonyl and aromatic quaternary carbons of terephthalate have different chemical shifts but identical relaxation times and nuclear Overhauser enhancements in the three different triad sequences. Peak areas indicate random copolymerization of the three copolyesters studied.     

Structural analysis of poly[(R,S)-3-hydroxybutyrate-co-L-lactide] copolyesters by electrospray ionization ion trap mass spectrometry

Two random copolyesters of poly[(R,S)-3-hydroxybutyrate-co-L-lactide] (P[(R,S)-3HB-co-LA]), prepared by equimolar reaction of (R,S)-beta-butyrolactone with L-lactic acid and (R,S)-3-hydroxybutyric acid with L-lactide, respectively, were characterized by electrospray ionization ion trap mass spectrometry (ESI-ITMS). Detailed studies of these copolyesters were performed by means of collision-induced dissociation (CID). The molecular architecture of individual copolyester macromolecules, including chemical structures of their end groups (hydroxyl and carboxylate), were established on the basis of their ESI mass spectra. The influence of an intermolecular transesterification reaction on the microstructure of the copolyester synthesized by equimolar reaction of (R,S)-3-hydroxybutyric acid with L-lactide was observed. The mass spectra provided information on sequence distribution and indicated that, despite the synthetic pathway applied, random P[(R,S)-3HB-co-LA] copolyesters were formed predominantly. The arrangements of comonomer structural units along the copolyester chains were evaluated by the respective ESI-MS/MS fragmentation pathways.     

Evolution of the structure of mesophase polyfluoroalk-oxyphosphazenes and liquid crystalline copolyesters

Comparative analysis of the temperature evolution of the structure of linear organoelement polyfluoroalkoxyphosphazenes and wholly aromatic main-chain copolyesters was carried out using X-ray analysis, differential scanning calorimetry and dynamic mechanical testing within a wide temperature range. Experimental observations show that flexible-chain polyfluoroalkoxyphosphazenes are inclined to formation of the columnar mesophase and condis crystalline structures, while rigid-chain random copolyesters mainly exhibit peculiar smectic and nematic liquid crystalline states.     

Poly(ethylene‐co‐1,4‐cyclohexylenedimethylene terephthalate) copolyesters obtained by ring opening polymerization

Cyclic oligomer fractions of ethylene terephthalate c(ET)_n and 1,4‐cyclohexylenedimethylene terephthalate c(CT)_n were obtained by cyclodepolymerization of their respective polyesters, the former containing around 80 mol % of trimer and the latter with around 70 mol % of trimer to pentamer. Mixtures of these fractions at selected compositions were subjected to ring opening copolymerization to give a series of poly(ethylene‐co‐cyclohexylenedimethylene terephthalate) copolyesters with ET/CT comonomer ratios ranging from 90/10 to 10/90. The copolyesters were characterized by GPC and NMR, and their thermal properties were evaluated by DSC and TGA. They had essentially the same composition as the feed from which they were produced and had an average‐weight molecular weights between 30,000 and 40,000 g/mol with polydispersities between 2 and 2.7. The distribution of the monomeric units in these copolyesters was essentially at random although it evolved to be a blocky microstructure as the contents in the two comonomers became more dissimilar. Their thermal behavior was the expected one for these types of copolyesters with crystallinity and heating stability decreasing with the content in CT units. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5954–5966, 2009     

Synthesis and characterization of fully aromatic thermotropic liquid‐crystalline copolyesters containing m‐hydroxybenzoic acid units

A series of fully aromatic copolyesters based on p‐acetoxybenzoic acid (p‐ABA), hydroquinone diacetate (HQDA), terephthalic acid (TPA), and m‐acetoxybenzoic acid (m‐ABA) were prepared by a modified melt‐polycondensation reaction. The copolyesters were characterized by DSC, thermogravimetric analysis, ¹H NMR, polarized optical microscopy, X‐ray diffraction, and intrinsic viscosity measurements. The copolyesters exhibited nematic liquid‐crystalline phases in a broad temperature range of about 150 °C, when the content of linear (p‐ABA, HQDA, and TPA) units was over 67 mol %. DSC analysis of the anisotropic copolyesters revealed broad endotherms associated with the nematic phases, and the melting or flow temperatures were found to be in the processable region. The flow temperatures and crystal‐to‐nematic and nematic‐to‐isotropic transitions depend on the type of linear monomer units, and these transitions increased as the content of the p‐ABA units increased, as compared to the HQDA/TPA units. When the content of the p‐ABA units increased, as compared to other linear units (HQDA and TPA), the intrinsic viscosity and degree of crystallinity of the copolyesters also increased, implying a higher reactivity for p‐ABA in the p‐ABA/HQDA/TPA/m‐ABA polymer system. The aromatic region in the ¹H NMR spectra of the copolyesters containing equal molar compositions of p‐ABA, HQDA, and TPA units were sensitive to the sequence distribution of aromatic rings. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3263–3277, 2001     

STUDIES ON THERMOTROPIC LIQUID CRYSTALLINE COPOLYESTERS:POLY (ARYLENE TEREPHTHALATECO-HEXAMETHYLENE TEREFHTHALATE)

A series of copolyesters based on terephthaloyl chloride, hexamethylene glycol and hydroquinone or chlorohydroquinone were prepared. The copolymers showed composition-dependent liquid crystalline properties as verified by visual observation of stir-opalescence, polarizing microscope and DSC. The copolyesters with aromatic diol contents over a certain extent (x≥0.2) were thermotropic with wide liquid crystalline temperature ranges. Comparing with the copolyesters based on butylene glycol or ethylene glycol, the minimum fraction of aromatic diol (x value) used to get the liquid crystallinity for all these copolyesters is around 0.2 regardless of the chain lengths of aliphatic glycols. ~1H-NMP studies revealed that copolyesters have microstructure of block sequence distribution and the mesogenie segments shorter than triad with three phenyl nuclei will not provide the liquid crystallinity.