Synthesis and eutectic behavior of liquid crystalline copolyesters

A series of liquid crystalline copolyesters, derived from 1,4‐hydroxy‐benzoic acid (HBA), 6‐hydroxy‐2‐naphthoic acid (HNA), terephthalic acid (TA), and hydroquinone (HQ), were prepared; crystallization, melting and solid‐state structure of the copolyesters were studied by using differential scanning calorimetry (DSC) and wide‐angle x‐ray diffraction (WAXD). It was found that the variation of melting point of the copolyesters with increasing HBA mol % exhibits eutectic melting behavior at a constant mole ratio of HNA, and the extrapolated eutectic temperature decreases linearly with increasing HNA mol %. WAXD analysis of the copolyesters indicates that the d‐spacing related to three‐dimensional order increases first and then decreases with increasing HBA mol %. The increase of the d‐spacing, consistent with looser packing of chains, leads to the reduction of melting point and most likely accounts for the eutectic behavior observed. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2171–2177, 2009     

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.     

Synthesis and Characterization of Block Copolymers of Poly(Butylenes Terephthalate-Co-Adipate)

The block copolyesters of poly(butylene terephthalate)(PBT) and poly(butylene adipate)(PBA) were prepared by a novel two-stage method. In the first stage, high molecular weight PBT and PBA were melt mixed in the presence of 1,4-butanediol at 275 °C. In the second stage, vacuum was applied to raise the molecular weight. The extent of transesterification was controlled by the proportion of 1,4-butanediol. The sequence distribution and the thermal properties of the block copolyesters were characterized by NMR and DSC respectively.     

Preparation and characterization of biodegradable aliphatic-aromatic copolyesters/nano-SiO_2 hybrids via in situ melt polycondensation

In situ melt polycondensation was proposed to prepare biodegradable aliphatic-aromatic copolyesters/nano-SiO_2 hybrids based on terephthalic acid(TPA),poly(L-lactic acid) oligomer(OLLA),1,4-butanediol(BDO) and nano-SiO_2.TEM and FT-IR characterizations confirmed that TPA,OLLA and BDO copolymerized to obtain biodegradable copolyesters,poly(burylene terephthalate-co-lactate)(PBTL),and the abundant hydroxyl groups on the surface of nano-SiO_2 provided potential sites for in situ grafting with the simultaneo...     

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.     

Synthesis, properties and enzymatic hydrolysis of biodegradable alicyclic/aliphatic copolyesters based on 1,3/1,4-cyclohexanedimethanol

This study synthesizes a series of cyclohexanedimethanol (CHDM)-based alicyclic/aliphatic copolyesters (PBSCs) using succinic acid, 1,4-butanediol and 1,3/1,4-CHDM at various molar ratios to investigate the effects of these compositions on crystallinity, biodegradability and the mechanical properties of PBSCs. The PBSCs were characterized using proton nuclear magnetic resonance, gel permeation chromatography, wide-angle X-ray diffraction, differential scanning calorimeter and thermogravimetric analysis. Biodegradability was evaluated by enzymatic hydrolysis with a lipase from Pseudomonas cepacia. The mechanical properties of PBSCs were determined using a tensile testing machine.Experimental results reveal that the PBSCs containing 1,3/1,4-CHDM in total diol with less than 50 mol% are crystallizable, while those containing 1,3/1,4-CHDM with more than 50 mol% are amorphous. The biodegradability test results suggest that PBSCs can be classified as surface-eroding polymers with a random endo-type scission. Surface hydrophilicity of PBSCs was the predominant effect on enzymatic hydrolysis, not crystallinity.     

Novel copolyesters based on poly(alkylene dicarboxylate)s: 2. Thermal behavior and biodegradation of fully aliphatic random copolymers containing 1,4-cyclohexylene rings

Aliphatic poly(butylene 1,12-dodecanedioate) is an interesting biodegradable polyester characterized by high thermal stability and high crystallinity, but low melting temperature. In order to improve the performances of this polymer some novel fully aliphatic random copolyesters have been prepared starting from 1,4-butanediol and different molar ratio of 1,12-dodecanedioc acid and 1,4-cyclohexanedicarboxylic acid. The copolymers have a notable resistance to thermal degradation, thermal properties which vary as a function of the composition, and maintain the mechanical characteristics of the poly(alkylene dicarboxylate). In particular, the copolymer containing the 70 mol% of 1,4-cyclohexanedicarboxylate units improves the thermal properties of the poly(butylene 1,12-dodecanedioate) and presents a very high biodegradation rate, higher than those of the two parent homopolymers. This behavior has been correlated to the low level of crystallinity of the sample and to the composition of the amorphous phase. Therefore, these novel fully aliphatic copolymers represent an interesting new class of copolyesters which can balance good physical properties and high biodegradability.     

生物可降解共聚物聚丁二酸/对苯二甲酸丁二醇酯(PBST)的序列结构及结晶性研究

制备了高分子量的聚丁二酸丁二醇酯,并通过与对苯二甲酸二甲酯的无规共聚调节其生物可降解性及力学性能,得到了具有优良机械性能和不同生物降解速度的一系列共聚物,并对共聚物序列结构、热力学性能、结晶性进行了研究.结果表明,该共聚物为无规共聚物,PBS和PBT分别结晶.共聚物的结晶熔点符合无规共聚物的Flory方程.     

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     

聚（琥珀酸丁二醇酯-共-富马酸丁二醇酯）的合成及其双羟基化反应研究

以琥珀酸、富马酸、丁二醇为原料，用共缩聚的方法合成了一系列高分子量聚 （琥珀酸丁二醇酯-共-富马酸丁二醇酯）。然后在催化剂四氧化锇和N-甲基吗啉- N-氧化物以及水存在下，使高分子主链中富马酸丁二醇酯共聚单元的碳碳不饱和双 键发生羟基化反应得到含有亲水性侧羟基的功能性聚酯。对上述合成的生物降解性 高分子运用核磁共振（NMR）、红外（FT-IR）、热分析等方法进行了结构与物理性 能表征。     

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     

New polymer synthesis. LXXXIII. Synthesis of chiral and cholesteric polyesters from silylated “sugar diols”

A series of polycondensation was conducted with the purpose to optimize the reaction conditions for the polycondensation of silylated 2,3-isopropylidene D -threitol with a dicarboxylic acid dichloride. Polycondensation in o-dichlorobenzene or 1-chloronaphthalene at 180–230°C were found to be most satisfactory. Trifluoroacetic acid/H₂O allow an easy cleavage of the isopropylidene group without hydrolysis of the polyester. Ten cholesteric copolyesters were prepared by polycondensation of mixtures of silylated methylhydroquinone and isosorbide, isomannide, or 2,3-isopropylidene threitol with the dichloride of 1,10-bis(4′-carboxyphenoxy)decane. All these copolyesters form a broad cholesteric phase above 200°C. The copolyesters containing 5 or 10 mol % of a sugar diol display a blue Grandjean texture. © 1996 John Wiley & Sons, Inc.     

Biodegradable poly(butylene succinate-<Emphasis Type="Italic">co</Emphasis>-butylene dimerized fatty acid)s: Synthesis,crystallization, mechanical properties,and rheology

Poly(butylene succinate-co-butylene dimerized fatty acid) (P(BS-co-BDFA)) copolyesters were synthesized from succinic acid (SA) and dimerized fatty acid (DFA) with 1,4-butanediol (BDO) through a two-step process of esterification and polycondensation. The polyester compositions and physical properties of copolyesters were investigated by GPC, ¹H NMR and ¹³C NMR, DSC, WAXD, DMA, TGA, tensile and rheology test. The melting temperature (T_m), and crystallization temperature (T_c) decreased gradually as the content of DFA monomer increased. P(BS-co-BDFA) copolyesters showed the same crystal structure as the PBS homopolyester. Besides, TGA results indicated that P(BS-co-BDFA)s were of higher thermal stabilities. Moreover, it was found that the synthesized P(BS-co-BDFA)s showed the maximum elongation at break (591%) as the DFA contents were 10 mol%. Rheology analysis indicated that the viscoelastic behavior of the polyesters greatly depended on the molecular weight of polyesters.     

Syntheses and Physical Characterization of Biodegradable Poly(butylene succinate-co-butylene itaconate) Copolymers

Biodegradable aliphatic poly (butylene succinate-co-butylene itaconate) (PBSBIs) from succinic acid, itaconic acid and 1,4-butanediol were synthesized through a polycondensation with titanium tetraisoproxide (TTP), diphenylphosphinic acid (DPPA) as the novel co-catalysts in this article. By means of gel permeation chromatography (GPC) and nuclear magnetic resonance spectrometer (NMR), it was revealed that the PBSI copolyesters had number average molecular weights M_n higher than 3.0 × 10⁴, and the composition of copolyesters was in good agreement with that expected from the feed composition of the reactants. With respect to thermal properties, melting temperature (T_m), crystallization temperature (T_c), and crystallinity (X_c) were found to decrease with increasing the BI/BS unit molar ratio up to 0.67. X-ray diffraction patterns indicated that the PBSIs copolyesters had the same crystal structure as the PBS. While increasing the BI/BS unit molar ratio up to 1, the copolyesters would change into insolubility and inmelt crosslinked elastomer. Otherwise, the observation of polarizing optical microscope (POM) showed that the spherulite size of copolyesters gradually became smaller with the increasing of BI unit content. Experimental results also showed that the contents of itaconic acid had an important effect on the biodegradable performance of copolyesters.     

Biosynthesis and Characterization of Poly (3-hydroxybutyrate-<Emphasis Type="Italic">co</Emphasis>-3-hydroxyvalerate-<Emphasis Type="Italic">co</Emphasis>-4-hydroxybutyrate) Terpolymer with Various Monomer Compositions by <Emphasis Type="Italic">Cupriavidus</Emphasis> sp. USMAA2-4

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-4-hydroxybutyrate) [P(3HB-co-3HV-co-4HB)] terpolymer was produced using Cupriavidus sp. USMAA2-4 via one-step cultivation process through combination of various carbon sources such as 1,4-butanediol or γ-butyrolactone with either 1-pentanol, valeric acid, or 1-propanol. Oleic acid was added to increase the biomass production. The composition of 3HV and 4HB monomers were greatly affected by the concentration of 1,4-butanediol and 1-pentanol. Terpolymers with 3HV and 4HB molar fractions ranging from 2 to 41 mol.% and 5 to 31 mol.%, respectively, were produced by varying the concentration of carbon precursors. The thermal and mechanical properties of the terpolymers containing different proportions of the constituent monomers were characterized using gel permeation chromatography (GPC), DSC, and tensile machine. GPC analysis showed that the molecular weights (M _w) of the terpolymer produced were within the range of 346 to 1,710 kDa. The monomer compositions of 3HV and 4HB were also found to have great influences on the thermal and mechanical properties of the terpolymer P(3HB-co-3HV-co-4HB) produced.     

Preparation and properties of poly(methylene terephthalates)

A systematic study of poly(methylene terephthalates) has been made. Melting points, second-order transition temperatures, and solubility temperatures are presented for the homologous series of terephthalate polyesters of ethylene glycol through 1,10-dodecanediol, and for terephthalate copolyesters of: (1) ethylene glycol/1,3-propanediol and (2) ethylene glycol/1,4-butanediol. Fiber properties of the terephthalate polyesters and the 70/30 ethylene glycol/1,3-propanediol copolyterephthalate ester are presented. Only the first three members of the poly(methylene terephthalate) series show promise for use in textile fibers.     

New polymer syntheses. 102. Aspirin‐modified LC polyesters based on PET and 4‐hydroxybenzoic acid

Four series of liquid‐crystalline copolyesters were prepared by the transesterification of poly(ethylene terephthalate) (PET) with 4‐acetoxybenzoic acid (4‐ABA) or mixtures of 4‐ABA and acetylsalicylic acid (ASA). Two series consisted of 30 mol % PET, and the other two series consisted of 40 mol % PET. The molar ratio of 4‐HBA and ASA was varied in all four series from 0 to 25 mol %. One 30% PET series and one 40% PET series were prepared with the addition of acetic acid, which caused a more perfect randomization of the sequence but yielded slightly lower molecular weights. The incorporation of ASA reduced the crystallinity, which vanished completely at a salicylic acid (SA) content greater than 10 mol %. SA also reduced the stability of the nematic phase, but all the copolyesters were thermotropic up to a 20 mol % SA content. Furthermore, the molecular weights decreased with the increasing incorporation of ASA. Despite this negative trend, the melt viscosity and the storage and loss moduli passed a maximum between 5 and 10% SA. Obviously, the incorporation of SA favored the formation of entanglements. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2013–2022, 2000     

Biodegradable liquid crystalline aromatic/aliphatic copolyesters. Part I: Synthesis, characterization, and hydrolytic degradation of poly(butylene succinate-co-butylene terephthaloyldioxy dibenzoates)

To increase the thermal and mechanical properties of the aliphatic polyester poly(butylene succinate) (PBS), a series of potentially biodegradable liquid crystalline aromatic/aliphatic random copolyesters were prepared by melt polycondensation of new mesogenic monomers dimethyl 4,4′-(terephthaloyldioxy) dibenzoate (MTB), dimethyl succinate, and 1,4-butanediol. The synthesized copolyesters were characterized by means of proton nuclear magnetic resonance spectroscopy (¹H NMR), gel permeation chromatography (GPC), viscosity measurements, differential scanning calorimetry (DSC), thermogravimetry (TG), X-ray diffraction (XRD), polarizing light microscopy (PLM) and mechanical property measurements. The MTB content was varied so that the effects of the mesogen content on the thermal and mechanical properties, degradable behaviours and mesophase were examined. It was found that introducing the rigid rod mesogens could increase the thermal stability and the mechanical properties, while it reduced the melting temperature (T_m), the crystallization temperature (T_c), the degree of relative crystallinity (X_c) and the hydrolytic degradation rate. Only the homopolyester poly(butylenes terephthaloyldioxy dibenzoates) was able to show the schlieren texture characteristic of nematics.     

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.     

Characterization of Deep Eutectic Solvents for Dispersive Liquid–Liquid Microextraction for Phenolics

Dispersive liquid–liquid microextraction using deep eutectic solvents, as novel extraction solvents, was developed for the separation, preconcentration, and determination of chlorophenol, 2,3-dihydroxybenzoic acid, p-cresol, 4-chlorophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol in vegetable oil. Seven deep eutectic solvents composed of choline chloride and different hydrogen bond donors (ethyl glycol, glycerol, 1,2-butanediol, 1,4-butanediol, 1,6-hexanediol, urea, and acetic acid) were characterized. The deep eutectic solvents formed by choline chloride-1,6-hexanediol in a 1:2 molar ratio provided the highest extraction efficiency. The sonication time, deep eutectic solvent volume, and disperser solvent were optimized. Under the optimal conditions of a sonication time of 11?min, a deep eutectic solvent volume of 90?µL, and acetone as the disperser solvent, extraction recoveries from 76.1 to 88.3% were obtained with 8.46 to 9.46 enrichment factors and the limits of detection exceeding 0.1?µg/mL with the relative standard deviations from 1.0 to 3.5%. This method using dispersive liquid–liquid microextraction with deep eutectic solvents is simple and provides high enrichment.