Synthesis and characterization of potentially biodegradable thermotropic polyesters based on p-hydroxybenzoic acid and glycolic acid

The synthesis of novel thermotropic liquid crystalline copolyesters derived from aliphatic hydroxy acid (glycolic acid, GA) and aromatic hydroxy acid (p-hydroxybenzoic acid, PHBA) via a melt-copolycondensation process in the presence of various catalysts was explored. The following three possible routes were checked: PHBA and GA in different feed ratios with or without a catalyst; PHBA and GA in different feed ratios with or without a catalyst in the presence of acetic anhydride as a condensation agent; and different PHBA derivatives were used to examine the reactivity of aromatic hydroxy acid. The copolycondensability, chemical structure, liquid crystallinity, textures and morphology, phase transition behaviors and thermal stability, and solubility were investigated by FTIR, NMR, DSC, TGA, and polarized-light microscope. It has been found that only the 60–70 mol % PHBA-containing copolyesters could exhibit a nematic liquid crystallinity. The as-prepared polymers were brittle due to relatively lower molecular weights. © 1994 John Wiley & Sons, Inc.     

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.     

Direct synthesis of potentially biodegradable aromatic–aliphatic thermotropic copolyesters with photocrosslinking properties

ABSTRACT

In this study, aromatic–aliphatic thermotropic copolyesters derived from p-hydroxybenzoic acid, p-hydroxycinnamic acid (HCA), terephthalic acid and polyethylene glycol (PEG) with different molecular weight (200, 400, 600) were directly synthesised via Vilsmeier adduct solution polymerisation method. The structure, thermal behaviour, liquid crystal property, hydrophylicity and photoactivity were investigated by Fourier transform infrared and nuclear magnetic resonance spectroscopy, differential scanning calorimeter, polarised optical microscopy, water contact angle measurement and ultraviolet (UV) spectrophotometer. The PEG incorporation ratio is 0.540–0.691 related to the HCA units, because of its low reactivity. And, the copolyesters have relatively low melting temperatures (96–107°C) and good hydrophylicity (water contact angle value 61.2–75.3°) as compared with wholly aromatic thermotropic copolyester. All of the copolyesters exhibited nematic liquid crystal behaviour and the stable mesophase temperature range was more than 60°C after being melted. The resulted copolyesters had enough thermal stability for melt processing without any degradation. The UV absorption intensities decreased with increased irradiation time, indicating that photocrosslinking occurred.     

Depression of the crystal-nematic phase transition in thermotropic liquid crystal copolyesters

The crystal-nematic phase transition of a copolyester consisting of 20 mol% poly(ethylene terephthalate) and 80 mol% p-hydroxybenzoic acid (PHB) was characterized by depression of the crystal-nematic transition by the addition of a liquid crystal diluent. This copolyester contains blocks of crystalline PHB. Its transition behavior was compared with thatrandom copolyester with diluent of the same composition. From the extrapolated transition temperature depression data, the heat of transition per mole of p-oxybenzoate was calculated as about 1.3 kcal/mol, with an entropy of about 2 cal/deg mol. This assumes that only the p-oxybenzoate unit crystallized from the nematic state. The validity of the Flory-Huggins model for this transition point depression was confirmed graphically by comparison with two different thermotropic-liquid crystal polyesters. These results may represent the first reported crystal-nematic temperatures and heats generated by the dilution method for liquid crystal copolyesters of this type.     

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.     

Thermal properties of random copolyesters of PET and 3- and 3,5-bromo-substituted p-hydroxybenzoic acids. II

Melt-polycondensation of poly(ethylene terephthalate) (PET) and 3-bromo-p-acetoxybenzoic acid or 3,5-dibromo-p-acetoxybenzoic acid in different mole ratios yielded random copolyesters. The copolyesters have higher T_gs than PET because of an increase in mol % of the substituted p-oxy-benzoate units and follow Wood's equation for copolymer T_gs. Using this equation, we calculated the T_gs of the homopolymers of 3-bromo-p-oxybenzoate and 3,5-dibromo-p-oxybenzoate, which are not available experimentally, to be 113 and 123°C, respectively. Up to certain percentages of the comonomer composition the copolyesters exhibited cold crystallization and melt transitions which we attribute to the crystallizable segments of PET. The variation in melting temperatures in the composition of the copolymer was explained by Flory's theory. The differences in the melting behavior of the polymer, annealed at various crystallization temperatures for a constant time interval, throws light on the morphological changes that took place in it. Using the Hoffman and Weeks method, we determined the extrapolated equilibrium melting temperatures of these copolyester which were used to calculate the enthalpy of melting for the crystallizable units.     

Study on poly(oxybenzoate-p-trimethylene terephthalate) copolymer

This study examined copolymers synthesized from poly(trimethylene terephthalate) (PTT) and p-acetoxybenzoic acid using solution proton nuclear magnetic resonance (NMR) spectroscopy. Proton NMR spectra showed that these p-oxybenzoate (POB)/PTT copolyesters were almost random copolymers because the preference factor of POB bonded to another POB unit in these copolyesters is close to 1.0 with a POB content between 20 and 80 mol%.The melting and crystallization behaviors of these copolyesters were studied by differential scanning calorimetry (DSC). In the heating DSC scan of the POB rich composition, the endothermic peak is weaker because the enthalpy of fusion decreased due to a melting transition from a crystalline to anisotropy liquid state. Thermogravimetric analysis results indicated that the decomposition temperature (T_d) increased with POB content. The crystalline morphology of the copolyester was further investigated with a polarized optical microscope, indicating that the POB/PTT copolyesters with 60 mol% POB are highly anisotropic in the liquid state.     

Thermally stimulated current and DSC studies of the broadened glass transition in liquid crystalline polymers

The high sensitivity of the thermally stimulated current, thermal sampling (TS) method is emphasized in a study of the breadth of the glass transition in several liquid-crystalline polymers (LCPs). Differential scanning calorimetry (DSC) was performed on all samples to further quantify the glass transition regions. For “random” copolyester LCPs with widely varying degrees of crystallinity, including highly amorphous samples, very broad glass tran-sition regions were observed. One semicrystalline alternating copolyester and a series of semicrystalline azomethine LCPs were studied as examples of structurally regular polymers. These exhibited relatively sharp glass transitions more comparable to ordinary isotropic amorphous or semicrystalline polymers. The broad glass transitions in the random copolyesters are attributed to structural heterogeneity of the chains. In one example of a moderate-crystallinity random copolyester LCP (Vectra), glass transitions ranging up to ca. 150°C in breadth were determined by the thermal sampling (TS) method and DSC. In other lower crystallinity copolyester LCPs, the main glass transition temperature as determined by DSC was comparable to that determined by TSC although cooperative relaxations of a minor fraction of the overall relaxing species were detected well below the main T_g, by the TS method and not by DSC. Rapid quenches from the isotropic melt to an isotropic glass were possible with one LCP. The anisotropic and isotropic glassy states for this LCP were found to have the same breadth of the glass transition as was determined by the TS method, although TSC and DSC show that T_g is shifted downward by ca. 15°C in the anisotropic glass as compared to the isotropic glass. © 1993 John Wiley & Sons, Inc.     

Carbohydrate‐based copolyesters made from bicyclic acetalized galactaric acid

Mixtures of the dimethyl esters of adipic acid and 2,3:4,5‐di‐O‐methylene‐galactaric acid (Galx) were made to react in the melt with either 1,6‐hexanediol or 1,12‐dodecanediol to produce linear polycyclic copolyesters with aldarate unit contents varying from 10 up to 90 mole %. The copolyesters had weight–average molecular weights in the ～35,000–45,000 g mol^?1 range and a random microstructure, and were thermally stable up to nearly 300 °C. They displayed T_g in the ‐50 to ‐7 °C range with values largely increasing with the content in galactarate units. All the copolyesters were semicrystalline with T_m between 20 and 90 °C but only those made from 1,12‐dodecanediol were able to crystallize from the melt at a crystallization rate that decreased as the contents in the two comonomers approached each other. Copolyesters containing minor amounts of galactarate units adopted the crystal structure characteristic of aliphatic polyesters but a new crystal polymorph was formed when the cyclic sugar units became the majority. Stress–strain parameters were sensitively affected by composition of the copolyesters with the mechanical behavior changing from flexible/ductile to stiff/brittle with the replacement of adipate units by the galactarate units. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

非晶聚对苯二甲酸乙二酯的制备与表征

通过单体酯交换法和聚 2 ,6 萘二甲酸乙二酯 (PEN)与低分子量PET酯交换的方法分别合成了一系列NPA/TPA/EG和IPA/TPA/EG共聚酯 .随着NPA或IPA单元含量的增加 ,等温结晶速度迅速降低 ,共聚物的结晶性降低甚至非晶化 .由NMR分析得知单体酯交换法与聚合物酯交换法得到的共聚酯NPA/TPA/EG序列分布相近 ,链结构都接近完全无规 .由DSC结果分析 ,随共聚单体含量的增加 ,熔点和熔融热降低 ,结晶度也随之降低 .当NPA或IPA含量达到 2 0 %时 ,可以得到非晶的共聚酯 (APET) .本文还对共聚物组成与结晶温度的关系进行了表征     

A facile preparation of microparticles from sulfonated polyester nanoparticles via emulsion–aggregation process

A process to prepare microparticles of narrow size distribution having a particle size in the range of approximately 1–8 μm was developed. The primary objective of this work was to study the formation and morphology of copolyester microparticles prepared using a sulfonated copolyester emulsion by an emulsion–aggregation process. Molecular weight of the copolyesters was measured by gel permeation chromatography. The glass transition temperature (T_g) of the copolyesters was found to be in the range of 40–70 °C. Aggregating agents used in this study were 1–5% (wt.%) solutions of divalent ions of zinc acetate and magnesium chloride salts. Emulsion–aggregation experiments were performed at various temperatures: 40, 50, 60, and 80 °C. Particle morphologies studied by field emission-scanning electron microscopy measurements provided an understanding of the conditions and mechanism leading to formation of microparticles by the emulsion–aggregation process. Molecular weight and T_g of the copolyester, the concentration of aggregating agent, and the temperature were determined to be the most important parameters influencing the preparation of microparticles. This process illustrates the preparation of microparticles of uniform size with morphology of controlled shape from a nanometer-sized emulsion by ionic crosslinking.     

一种基于联苯二甲酸为介晶基元的含磷液晶共聚酯的合成与表征

以联苯二甲酸二甲酯、二甘醇和9,10-二氢-9-氧杂-10磷酰杂菲-对苯二酚二羟乙基醚(DOPO-HQ-HE)为单体,通过无规共聚合成了一种新型含磷液晶共聚酯(PDEBP).用1H-NMR对共聚酯的结构进行了表征,用TGA、DSC和POM对其热性能及液晶行为进行了研究.结果表明,阻燃单体DOPO-HQ-HE的引入不会降低共聚酯的热稳定性,含7.5 mol％ DOPO-HQ-HE的共聚酯PDEBP7.5在700℃的氮气氛中的残余物(Wt700R)可达31.9 wt％,并且具有很好的阻燃性.DOPO-HQ-HE含量的增加对共聚酯的结晶性有较大的破坏,5 mol％ DOPO-HQ-HE的共聚酯PDEBP5的清亮点温度为154.2℃,焓变为4.64 J/g,而PDEBP7.5在POM测试中在升温及降温过程中均难观察到液晶相的双折射现象.     

Synthesis and properties of novel photocrosslinkable aromatic-aliphatic liquid crystal copolyesters based on poly(ethylene glycol) and cinnamic acid

Firstly, PEGn-TA monomers with carboxyl functional groups were synthesised by terephthalic acid (TA) and poly(ethylene glycol) (PEG) with molecular weight of 200, 400 and 600. Then, photocrosslinkable thermotropic liquid crystal copolyesters derived from PEGn-TA, 4,4?-biphenol, 4-hydroxy-cinnamic acid and 4-hydroxy-benzoic acid were successfully obtained by Vilsmeier adduct solution polymerisation method. Influence of PEG molecular weight on thermal behaviour, liquid crystal mesophase, hydrophilicity, structure and photoactivity were investigated by various measurements. Experimental results indicated that all copolyesters showed nematic mesophase textures, relative low melting temperatures, and two glass transitions as well as better hydrophilicity were observed for those contained higher PEG molecular weight. Photocrosslinking rate was increased first and then decreased due to effect of flexible PEG moieties. The resulted copolyesters with liquid crystal behaviour, excellent hydrophilicity and photoactivity could be potentially used as biomaterial.     

聚对苯二甲酸乙二酯(PET)/聚对乙酰氧基甲酸(PHB)共聚酯及同类共聚物序列分布表征的数学统计

 由聚对苯二甲酸乙二酯(PET)和对-乙酰氧基苯甲酸制得的PET/PHB共聚酯代表了一类序列结构较一般二元共聚物复杂的共聚体系.在揭示了这类共聚物与序列分布有关的诸概率参数中只有一个是独立的之后,定义了参数B_q来描述此类共聚物的无规度.并指出,共聚物B_q=b时的序列分布,可以从一般二元共聚物无规度B=b时的序列结构加以推断.     

CRYSTALLIZATION BEHAVIOR OF A THERMOTROPIC LIQUID CRYSTAL COPOLYESTER

A thermotropic liquid crystal copolyester resin based on p-hydroxybenzoic acid, 2, 6-naphthoic acid, hydroxyquinone and PET was synthesized by melt condensation and studied. The results based on DSC and X-ray diffraction indicated that there were a rapid and a slow crystallization processes for the copolyester at certain conditions. A critical temperature was suggested, below which the slow crystallization could hardly happen. Above the critical temperature the extent of the slow crystallization process depended not only on annealing temperature but also on the annealing time. A fine crystal structure with high melting point and narrow diffraction peak was formed under favorable conditions.     

Multiphase structure of segmented polyurethanes: Its relation with spherulite structure

Small-angle light-scattering (SALS), Polarized light microscopy (PLM), differntial scanning calorimetry (DSC), and small-angle x-ray scattering (SAXS) were used to study morphological changes in segmented polyurethanes with 4,4′-diphenylmethane diisocyanate (MDI) and 1,4-butanediol (BD) as the hard segment. It was found. for the first time, that spherulites could form from the melt by quenching the polyurethanes in the melt state to annealing temperatures between 120°C and T_h, the highest annealing temperature for spherulite formation. T_h ranged from 140°C to ca. 170°C and depended upon the hard-and soft-segment compatibility. Within the range 120°C to T_h, the radius of the spherulite increased with increasing hard-segment content at each fixed annealing temperature. Annealing at 135–140°C gave rise to the largest spherulites. SAXS was used to investigate the phase-separated structures corresponding to the spherulite formation. The interdomain spacing increased with increasing hard-segment content and with increasing annealing temperature.The degree of phase separation first increased with increasing annealing temperature from room temperatures (ca. 25°C), reached a maximum at ca. 107°C, and then decreased with further increase in the annealing temperature. On the basis of these observations, the mechanisms of phase separation, crystallization, and spherulite formation are discussed. © 1993 John Wiley & Sons, Inc.     

Melt transesterification and characterization of segmented block copolyesters containing 2,2,4,4‐tetramethyl‐1,3‐cyclobutanediol

Conventional melt transesterification successfully produced high‐molecular‐weight segmented copolyesters. A rigid, high‐T_g polyester precursor containing the cycloaliphatic monomers, 2,2,4,4‐tetramethyl‐1,3‐cyclobutanediol, and dimethyl‐1,4‐cyclohexane dicarboxylate allowed molecular weight control and hydroxyl difunctionality through monomer stoichiometric imbalance in the presence of a tin catalyst. Subsequent polymerization of a 4000 g/mol polyol with monomers comprising the low‐T_g block yielded high‐molecular‐weight polymers that exhibited enhanced mechanical properties compared to a nonsegmented copolyester controls and soft segment homopolymers. Reaction between the polyester polyol precursor and a primary or secondary alcohol at melt polymerization temperatures revealed reduced transesterification of the polyester hard segment because of enhanced steric hindrance adjacent to the ester linkages. Differential scanning calorimetry, dynamic mechanical analysis, and tensile testing of the copolyesters supported the formation of a segmented multiblock architecture. Further investigations with atomic force microscopy uncovered unique needle‐like, interconnected, microphase separated surface morphologies. Small‐angle X‐ray scattering confirmed the presence of microphase separation in the segmented copolyesters bulk morphology. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Fully aromatic thermotropic liquid crystalline polyesters of 3-phenyl-4,4′-biphenol with 4,4′-benzophenone dicarboxylic acid

A series of fully aromatic, thermotropic polyesters, derived from 3-phenyl-4,4′-biphenol (MPBP), nonlinear 4,4′-benzophenone dicarboxylic acid (4,4′-BDA), and various other comonomers was prepared by the melt polycondensation method and characterized for their thermotropic liquid crystalline behavior by a variety of experimental techniques. The homopolymer of MPBP with 4,4′-BDA had a fusion temperature (T_f) at 240°C, exhibited a nematic liquid crystalline phase, and had a narrow liquid crystalline range of 60°C. All of the copolyesters of MPBP with 4,4′-BDA and either 30 mol % 4-hydroxybenzoic acid (HBA), 6-hydroxy-2-naphthoic acid (HNA) or 50 mol % terephthalic acid (TA), 2,6-naphthale-nedicarboxylic acid (2,6-NDA) and low T_f values in the range of 210–230°C, exhibited a nematic phase, and had accessible isotropization transitions (T_i) in the range of 320–420°C, respectively. As expected, each of them had a broader range of liquid crystalline phase than the homopolymer. They had a “frozen” nematic, glassy order as determined with the wide-angle X-ray diffraction (WAXD) studies. The morphology of each of the “as-made” polyesters had a fibrous structure as determined with the scanning electron microscopy (SEM), which arises because of the liquid crystalline domains. Moreover, they had higher glass transition temperatures (T_g) in the range of 167–190°C than those of other liquid crystalline polyesters, and excellent thermal stabilities (T_d) in the range of 500–533°C, respectively. © 1995 John Wiley & Sons, Inc.     

Property relationships in dimer acid-modified copolyesters of poly(1,4-cyclohexylene dimethylene terephthalate) and poly(1,4-cyclohexylene dimethylene 1,4-cyclohexane dicarboxylate)

Dimer acid (D) modified copolyesters based on 1,4-cyclohexane dimethanol (CHDM) and either terephthalic acid (T) or trans-1,4-cyclohexane dicarboxylic acid (C) were examined. Both series produced clear, flexible materials with physical properties changing regularly with changing modifier levels. Yield stress, elongation at break, and Young's modulus showed linear correlations of log property versus volume fraction of CHDM-D segments in accord with the logarithmic rule of mixtures. Annealing the CHDM-T-based copolyesters caused little or no change in properties. Annealing the CHDM-C-based copolyesters gave similar results except for a large decrease in the modulus—the higher the dimer acid level, the larger the decrease in modulus. The density measurements, the x-ray pattern, and the dynamic mechanical analysis at 110 Hz before and after the annealing treatment supported the hypothesis that the modulus decrease resulted from domain perfection in the copolyester induced by the annealing process. Transmission electron-microscope examination of osmium tetroxide-stained films supported this hypothesis, although initial results were not repeatable.     

Liquid crystal polymers. VIII. Liquid crystalline polyesters of trans-4,4′-stilbenedicarboxylic acid and 1,3-propanediol

In our recent overview of liquid crystalline polyesters of trans-4,4′-stilbenedicarboxylic acid (SDA) and aliphatic glycols,¹ we reported that “… the 1,3-propanediol polyester did not exhibit thermotropic liquid crystallinity (no stir opalescence or DSC endotherm above T_m), perhaps because of the relatively high T_m (303°C) for a polymer of a glycol having an odd number of carbon atoms.” We now have studied the melting characteristics of another sample of this polymer more carefully and have concluded that it does exhibit a liquid crystalline mesophase over a very narrow temperature range. In this Note we give the thermal properties of this polymer and the thermal and mechanical properties of an SDA/1,3-propanediol copolyester which we also injection molded. These properties are compared and contrasted with those of the similar polyester and copolyester prepared with 1,4-butanediol instead of 1,3-propanediol.