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-SiO2 hybrids based on terephthalic acid （TPA）, poly（L-lactic acid） oligomer （OLLA）, 1,4-butanediol （BDO） and nano-SiO2. TEM and FT-IR characterizations confirmed that TPA, OLLA and BDO copolymerized to obtain biodegradable copolyesters, poly（butylene terepbthalate-co-lactate） （PBTL）, and the abundant hydroxyl groups on the surface of nano-SiO2 provided potential sites for in situ grafting with the simultaneous resulted PBTL. The nano-SiO2 particles were chemically wrapped with PBTL to form PBTL/nano- SiO2 hybrids. Due to the good dispersion and interfacial adhesion of nano-SiO2 particles with the copolyester matrix, the tensile strength and the Young＇s modulus increased from 5.4 and 5.6 MPa for neat PBTL to 16 and 390 MPa for PBTL/nano-SiO2 hybrids with 5 wt.% nano-SiO2, respectively. The mechanical properties of PBTL/nano-SiO2 hybrids were substantially improved.

Synthesis and Characterization of Novel Hydrolytically Degradable Polyesters

Six novel hydrolytically degradable polyesters were synthesized from thiodipropionic acid(TDPA)and five diols by melt polycondensation,and characterized by FT-IR,1H NMR,gel permeation chromatography,differential scanning calorimetry and thermogravimetry analysis.The polystyrene-equivalent number-average(Mn)and weight-average molecular weight(Mw)of these polyesters ranged from 4900-11100 Da and 7900-20879 Da,respectively,with PDI values of 1.48-1.98.The melting point varied from 62.3-127.9℃,and the 50%mass-loss temperature ranged between 387-417℃.The degradation of these polyesters was studied in terms of relative weight loss in distilled water at different pH.Weight losses of 14%-26%were obtained at pH 7.0,26%-38%at pH 6.0,and 32%-43%at pH 8.3 over a 20-week period.The ecotoxicity study suggested that safety of the synthesized polyesters for the eisenia foetida.These results indicate that these polyesters have a combination of good thermal and degradability behaviors,which can be tailored through selection of the diol monomers used in the synthesis.

Study on Structure and Crystallinity of A New Biodegradable Aliphatic-Aromatic Copolyester

A series of biodegradable aliphatic-aromatic copolyesters, poly(butylene terephthalate-co-butylene adipate-co- ethylene terephthalate-co-ethylene adipate) (PBATE), were synthesized from terephthalic acid (PTA), adipic acid (AA), 1,4-butanediol (BG) and ethylene glycol (EG) through direct esterification and polycondensation. The sequence structure and crystallinity of the copolyester were investigated by 1H NMR spectroscopy and the wide-angle X-ray diffractometry (WAXD). The analytical results showed that the PBATE copolyester was a random copolymer and the composition of PBATE copolyester was almost consistent with the feed molar ratios. The crystal structure of PBATE copolyester belonged to the triclinic crystalline system; The variation in melting point of the synthesized PBATE copolyester agreed well with the estimation obtained by the Flory equation and was applicable to the random copolymer.

Preparation of Durable Antibacterial Polyester Fabrics by Grafting with the Natural Quaternary Ammonium Compound Betaine

Recently, the textile industry has increasingly advocated for natural resource-based healthcare textiles. This research presents a facile and eco-friendly approach to developing durable antibacterial polyester fabrics. Polyester fabric was first subjected to an alkaline hydrolysis to impart hydroxyl groups on the fiber surface. A natural antibacterial agent, betaine, was then covalently bonded to the hydrolyzed polyester fiber surface through esterification. XPS, Raman, SEM, and Wicking measurements were carried out to verify the esterification reaction. Antibacterial tests confirmed that betaine treatment grafted polyester fabrics revealed a remarkable antibacterial effect with inhibition rates > 99.9% against both E. coli and S. aureus and still remained inhibition rates of up to 91.5% against both bacteria after home washing for 20 cycles. Moreover, the modification significantly increased the capillary effect of polyester fabric but did not cause apparent adverse effects on the fabric’s hand or tensile strength. Overall, this grafting strategy for durable, antibacterial polyester fabric represents a significant practicality in the textile industry.

SYNTHESIS AND CHARAOTERIZATION OF NOVEL THERMOTROPIO LIQUID ORYSTALLINE POLYESTERS BEARING NONLINEAR OPTICAL AZOBENZENE SIDE GROUP

A series of novel thermotropic liquid crystalline polyesters bearing nonlinear optical azobenzene side group were synthesized by high temperature solution polycondensation and their structures,thermal stability, phase transition behavior and crystallinity were characterized by IR,elemental analysis, TG-DTA, polarizing optical microscope (POM) equipped with a hot stage and X-ray diffraction techniques. The results demonstrate that all the synthesized polyesters exhibit nematic liquid crystalline phases and show relatively high glass transition temperatures and good thermal stability.

New thermally stable polyesters based on 2,5-pyridinedicarbonyl dichloride and aromatic diols:Synthesis and characterization

Six new thermally stable polyesters （4a-f） were synthesized through the solution polycondensation reaction of 2,5-pyridine dicarbonyldichloride （2） with six aromatic diols in N,N＇-dimethyl acetamide （DMAc） solution and in the presence of pyridine as a base. The polycondensation reactions produce a series of new polyesters （4a-f） in high yields, and inherent viscosity between 0.30 and 0.55 dL/g. The resulting polyesters were characterized by elemental analysis, viscosity measurements, thermal gravimetric analysis （TGA and DTG）, solubility test, Fourier transform infrared （FT-IR） spectroscopy and gel permeation chromatography （GPC）. C 2009 Khalil Faghihi. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

POLY (β-HYDROXYALKANOATES): NATURAL BIOCOMPATIBLE AND BIODEGRADABLE POLYESTERS PRODUCED BY BACTERIA

A wide variety of different types of microorganisms are known to produce intracellular energy and carbon storage products, which have been generally described as being poly (β-hydroxybutyrate), PHB, but which are, more often than not, copolymers containing different alkyl groups at the β-position. Hence, PHB belongs to the family ofpoly (β-hydroxyalkanoastes), PHA, all of which are usually formed as intracellular inclusions in bacteria under unbalanced growth conditions. Recently, it became of industrial interest to evaluate these PHA polyesters as natural biodegradable and biocompatible plastics for a wide range of possible applications, such as surgical sutures or packaging containers. For industrial applications, the controlled incorporation of repeating units with different chain lengths into a series of copolymers is desirable in order to produce polyesters with a range of material properties because physical and chemical characteristics depend strongly on the polymer composition. Such 'tailor-made' copolymers can be produced under controlled growth conditions in that, if a defined mixture of substrates for a certain type of microorganisms is supplied, a well defined and reproducible copolymer is formed.

Degradable Polyesters based on Oxygenated Fatty Acid Monomer

A series of degradable polyesters was synthesized via melt polymerization of 3,6-dioxaoctane-1,8-dioic acid and five different diols,catalyzed by antimony trioxide(Sb_(2)O_(3)).The polymers were characterized by FT-IR and ^(1)H NMR spectroscopy,gel permeation chromatography(GPC)and differential scanning calorimetry(DSC)analysis.The polydispersity index(PDI=M_(w)/M_(n))of the polyesters ranged from 1.55 to 1.99,the weight-average molecular weight(M_(w))from 1.8×10^(4) to 3.2×10^(4) Da,the melting point from 63 to 123℃,and the highest decomposition temperature observed was 363℃.The influence of the structure of the polymer chain on hydrolytic degradability was investigated with tests performed at three different values of pH.The findings obtained provide useful insight for the molecular design and the synthesis of degradable polyesters.

Synthesis and characterization of biodegradable aliphatic polyesters using dibutylmagnesium as initiator

Aliphatic polyesters were synthesized via the ring opening polymerization of the corresponding lactones initiated with dibutylmagnesium both in bulk and in solution. The resulting polymers were characterized by 1H, 13C NMR, GPC and XRD. The results indicated that dibutylmagnesium is an effective initiator for the ring opening polymerization of lactones.

Preliminary Study on Lipase-catalyzed Synthesis of Polyesters Containing L-Malic Acid Units

Terpolymer of 1, 8-octanediol, adipic acid, and L-malic acid was synthesized via a lipase-catalyzed direct polycondensation. The products were characterized by GPC and 1H NMR. The results indicated that the molecular weight of the prepared polymers decreased with increasing L-malic acid content in the monomer feed ratio, and that change in the L-malic acid content from 0 to 20 mol % did not remarkably influenced on the molecular weight distribution Mw /Ma of the prepared samples. The 1H NMR spectra of the obtained copolymer samples showed that hydroxyl groups of L-malic acid did not take part in the polymerization reaction.

An IR Study of the Dispersion Stability of Catalyst Powders Dispersed in Solutions of Linear Saturated Polyesters

The conformation of polymers at the solid-liquid interface has been the subject of considerable interest in the fundamental theory and applied practice. In paints and printing inks, dispersions of pigment or filler powders in polymeric binder solutions have to be maintained in the colloidal state. One of the stabilizing mechanisms for paint is the steric stabilization. On the other hand, in the formation reaction of polymer at the solid-liquid interface took place between monomer solutions and solid

ADVANCES IN LIQUID CRYSTALLINE POLYESTERS

Advances have been made in understanding the interactions of composition, molecular weight, liquid crystallinity,orientation, and three-dimensional crystallinity on the properties of injection-molded and melt-spun liquid crystalline polyesters (LCP's). Two classes of potentially low-cost LCP's were compared:(1) semiflexible LCP's prepared from 1,6-hexanediol and the dimethyl ester of either trans-4, 4'stilbenedicarboxylic acid or 4.4 ' biphenyldicarboxylic acid and (2) all-aromatic LCP's prepared from terephthalic acid, 2, 6-naphthalenedicarboxylic acid, the diacetate of hydroquinone, and the acetate of p-hydroxybenzoic acid. The effects of composition on the plastic properties of the 4-component all-aromatic LCP's were determined with the aid of a 3 x 3 factorial statistically designed experiment, the generation of equations with a computer program, and the plotting of three-dimensional figures and contour diagrams. The effects of absolute molecular weight (M_w) on the tensile strengths of the semiflexible LCP's and one of the all-aromatic LCP's having an excellent balance of plastic properties were also compared, and it was observed that the semiflexible LCP's required M_w's about 4 times higher than the all-aromatic LCP to attain a given strength. Persistence lengths and molecular modeling were used to explain these differences.

A DSC STUDY OF PHOTOPOLYMERIZATION OF POLYESTERS CONTAINING CONJUGATED DIACETYLENES

The photopolymerization of two kinds of prepolyesters containing conjugated diacetylene (PDA-6 and PDA-12) was investigated using DSC. By measuring the endothermic enthalpy of the prepolymers after different UV-irradiation times, the polymerizations were found to follow the first-order rate law which agreed with the results of other investigators using a different method. The endothermic enthalpy measurements of PDA-6 and PDA-12 before UV-irradiation precluded the possibility that the decrease of endothermic enthalpy was caused by thermal polymerization.

STUDY ON THE BLENDS OF NYLON 66 AND LIQUID CRYSTALLINE POLYESTERS

Blends of polyamide (Nylon 66) with two different kinds of liquid crystalline polyesters were studied in all the composition range. Homogeneous samples were obtained by coprccipitation from 2 wt%. solution of blends. The thermal properties, crystallinity and morphology of these blends were studied by using DSC, polarizing microscopy, and scanning electron microscopy. The phase transition and morphology of the blends are markedly-influenced by the composition of liquid crystalline polyesters. The mechanical behaviour of PHB/HNA-Nylon 66 blend was improved. although polyamidc (Nylon 66)with the liquid crystalline polyesters were incompatible, but a rather strong interaction between the polymers did exist.

Synthesis and characterization of new polyesters based on 2,5-bis[(4-chloro carboxyanilino)carbonyl]pyridine and aromatic diols

Six new polyesters 7a-f were synthesized through the solution polycondensation reaction of diacid chloride 5 with six aromatic diols 6a-f in N,N-dimethyl acetamide(DMAc) as solvent in the presence of pyridine as base.The polycondensation reaction produced a series of novel polyester containing pyridyl moiety in the main chain in high yields with inherent viscosities between 0.35 and 0.54 dL/g.The resulted polymers were fully characterized by means of FT-IR spectroscopy,elemental analyses,inherent viscosity ...

FOURIER TRANSFORM INFRARED STUDY OF FRACTIONATED AROMATIC POLYESTERS

Infrared spectra at different temperatures have been studied for fractions ofa liquid crystal tormmg aromatic polyester. The molecular interactions in different phases and their changes duringthe transitions were discussed. Abrupt frequency shift was found for bands of groups both in mesogens and flexible spacers during fusion and isotropization transitions. It may imply that both the mesogens and the flexible spacers are included in the same crystalline phase and give their contributions to the formation of the mesophase. The splitting into doublet of the C—O stretching vibrations was observed for both the aromatic and aliphatic esters and was attributed to the existence of local regions for ester groups different in ordering. The more ordered regions do not disappear completely even in the isotropic liquid phase.

THE EFFECT OF SUBSTITUENT ON THE THERMAL PROPERTIES OF POLYESTERS CONSISTING OF AROMATIC TYPE SCHIFF BASE MESOGENIC UNITS AND POLYMETHYLENE SPACERS

Polyesters consisting of substituted aromatic type Schiff base mesogenic unit andpolymethylene spacers were synthesized and their thermal transitions and liquid crystallineproperties were studied. The liquid crystalline behaviour has been characterized by differentialscanning calorimetry (DSC) and optical polarizing microscopy. Structural broadening bysubstitution of methoxy group in 2, 2' positions of the mesogenic core produce polymers withlower transition temperatures. Polymers synthesized from ortho and meta substituted phenylenediamine did not form a liquid crystal phase.

Photopolymerization of Dendritic Acrylated Aromatic/Aliphatic Polyesters and Properties of Their Cured Films

The radiative curable dendritic acrylated aromatic/aliphatic polyesters based on pentaerythritol, 1,2,4 benzenetricaboxylic anhydride and epoxy propane modified with acryloyl chloride were synthesized via a divergent procedure, and their photopolymerization kinetics was studied by photo differential scanning calorimetry. The mechanical properties and the morphology of the fracture surface of the cured dendritic polyester films were investigated by means of dynamic mechanical thermal analysis and scanning electron microscopy, respectively.

Removal of Hydrophobic Organic Contaminants from Aqueous Solutions by Sorption onto Biodegradable Polyesters

Sorption by biodegradable polyesters of several aromatic chemicals as model compounds for hydrophobic organic contaminants (HOCs) was studied. The biodegradable polyesters used were poly(butylene succinate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate), poly(ε-caprolactone), poly(butylene succinate/ terephthalate), and poly(L-lactic acid). Petrochemical plastics, low-density polyethylene and polyethylene terephtalate, were used for comparison. The target HOCs were biphenyl, bisphenol-A, dibenzofuran, diethylstilbestrol, nonyl-phenol, and chlorophenols. The treatment of the HOC solutions with each of the biodegradable polyesters resulted in the nearly complete removal of the chemicals by sorption from the aqueous phase, except for the case of poly(L-lactic acid). Low-density polyethylene adsorbed biphenyl and dibenzofuran selectively, and polyethylene terephtalate did not adsorb any of the HOCs. The adsorptive interaction between the plastics and the HOCs might be related to both the glass transition temperature of the former and the nature of the latter as defined by the Fujita's inorganicity/organicity ratio. The toxic effect of 3,5-dichlorophenol on bacte-rial growth in liquid culture was removed by the addition of a biodegradable polyester. These results provide a basis for the applicability of the biodegradable plastics as the adsorbents for the removal of HOCs from aquatic environments.

SYNTHESIS AND CHARACTERIZATION OF LIQUID CRYSTAL POLYESTERS WITH T-SHAPED TWO-DIMENSIONAL MESOGENIC UNITS(Ⅲ)

A new series of liquid crystal polyesters with T-shaped two-dimensional mesogenic units weresynthesized by melt polycondensation of the diacetates of 2-(4'-alkoxy -phenyl)-hydroquinones with 4,4'-alkylenedioxydibenzoic acid. The polymers were characterized by using polarized microscopy, DSC and X-ray diffraction. It was realized that all the polymers have nematic thermotropic liquid crystallinecharacteristics. The melting temperature (T_m) and isotropization temperature (T_i) of the polymers changeregularly with varying lengths of the alkoxy side group and the length of the alkylene group in the main chainin company with an even-odd effect. The mesophase temperature range also varies regularly with the polymerstructure. It is shown that the mesophase range has been widened.