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.

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.

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.

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.

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 ...

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.

SYNTHESES AND CHARACTERIZATION OF A NEW TYPE OF LIQUID CRYSTALLINE POLYESTERS

A new type of liquid crystalline polyesters with resorcin as one part of the mesogenic unitconnected together by polymethylene, or phenylene group, and lateral groups consisting of arigid azobenzene as another part of the mesogenic unit were synthesized by interfacialpolymerization of diacyl chlorides in 1, 2-dichloroethane and 2, 4-dihydroxy-4'-nitroazobenzen inaqueous alkaline solution. The polyester structures were confirmed by proton NMR and IRspectra. Their phase transition behavior and texture were studied by polarizing microscopy andDSC.

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.

SYNTHESIS OF MESOGENIC POLYESTERS WITH 2-DICHLOROMETHYLHYDROQUINONE MOIETIES

A series of novel mesogenic polyesters with 2-dichloromethylhydroquinone moieties were synthesized by polycondensation of the novel diacyl chloride monomer 2-dichloromethyl-1,4-bis (4'-chloroformylbenzoyl) oxybenzene (I) with alpha, omega-polymethylenediols including ethylene glycol, 1,4-butanediol, 1,6-hexanediol and 1,10-decanediol. The diacyl chloride monomer was synthesized by simultaneous transformations of both the carboxy and formaldehyde groups of 2-formyl-1,4-bis (4'-carboxybenzoyl) oxybenzene into acyl chloride and dichloromethyl groups respectively. The syntheses of the monomer (I) and the polymers were reported.

Studying the Curing Conditions of Unsaturated Polyesters from Secondary Polyethylene Terephthalate Alcoholysis Products

The technological properties of the curing conditions for unsaturated polyesters synthesized on the basis of the alcoholysis products of secondary polyethylene terephthalate and unsaturated polyesters used in the production of fiberglass pipes were studied. It is shown that unsaturated polyesters synthesized on the basis of alcoholysis products can completely replace imported resins of grades 196 and 196A in the production of fiberglass pipes.

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.

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.

Synergetic organocatalysis for stereoregular ring-opening polymerization of O-carboxyanhydrides to isotactic functionalized polyesters

Polyesters,such as polylactide(PLA),are a class of biodegra-dable and biocompatible polymers that have received increasing attention in biomedicine,agriculture,and commodity thermoplastics[1-2].However,the lack of pendant functionality of conventional polyesters makes it difficult to modify and modulate the physicochemical properties in subsequent applications[3-4].Since 2006[5],the ring-opening polymerization(ROP)of O-carbox-yanhydrides(OCAs),which can be readily synthesized from amino acid or hydroxyl acid precursors,has been recognized as a promising route to functionalized polyesters[3-4].However,due to the increased methine C-H acidity,significant racemization of the stereogenic center and decreased stereoregularity have been identified for most OCAs,for instance,ManOCA[6](OCA from mandelic acid)and SerOCA[7](OCA from serine),when using typical 4-(dimethylamino)pyridine(DMAP)as catalyst.To minimize epimerization,some classical metal-based catalysts of coordination polymerization have been introduced to mediate ROP of OCAs,furnishing isotactic polyesters[8].

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.

Silicone Modified Polyesters Vulcanizable at Room Temperature for Anti-corrosion Coatings on Tinplate

Trimethoxysilyl Polyester(TMOS-PET)was prepared via hydrosilylation of trimethylsilane with acryl-terminated polyester.Copolymerization of TMOS-PET with trimethylmethoxysilane,tetramethoxysilane,and/or dimethyldimethoxysilane give silicone modified polyesters(Si-PET)containing=(SiO_(2))=,-(CH_(3)SiO_(3/2))=,and/or-((CH_(3))_(2)SiO)-units.Coatings from Si-PET were formed on tinplate surface via room temperature vulcanization with applicable curing time(the quickest tact free time and completely drying time are 2 h and 15 h,respectively).Mechanical properties,thermal stability,chemical resistance,and anti-corrosion of coatings were detected.Although the flexibility of the coatings were lowered by=(SiO_(2))=and-(CH_(3)SiO_(3/2))=units,adhesion and thermal stability of coatings were both improved.On the contrary,(CH_(3))_(2)SiOunits seem to improve the flexibility,while decrease the adhesive force for less crosslink points.Generally,the silicone modified polyesters act as an effective shielding for tinplate.According to electrochemical impedance spectroscopy(EIS),the electric resistance of coatings(Rc)were improved about 25 times and open circuit potential(OCP)increased about 0.10 V compared to the control.The chemical resistance and anti-corrosion of the coatings were decreased slightly after=(SiO_(2))=and-(CH_(3)SiO_(3/2))=units were added,but they could be greatly improved by-(CH_(3)SiO_(3/2))=units.Specially,after adding-(CH_(3)SiO_(3/2))=units,coatings give doubled Rc,and its OCP is about 0.20 V higher than the control.

CRYSTALLINE MORPHOLOGY IN A SERIES OF CH3-SUBSTITUTED THERMOTROPIC AROMATIC POLYESTERS WITH EVEN AND ODD FLEXIBLE SPACERS

Crystalline morphology in a series of CH3-substituted main chain thermotropic aromatic polyesters with even and odd numbered methylene spacers has been studied by polarizing optical microscopy (POM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). On crystallization from solution evaporation spherulites of radial structure were observed in the polymers with even numbered spacers, but spherulites with concentric rings form in the polymer with odd numbered spacers. Both spherulites have a lamellar structure, which is about 10 nm in thickness. On crystallization from nematic glassy state spherulites can not be grown; lamellar structure was only observed around disclinations in a specimen during crystallization. Ln the case of crystallization from nematic melt two types of spherulites can be observed far the sample with even numbered spacers. For the sample with add numbered spacers spherulites can not be formed, but only irregular crystallites.

Polyisocyanuratoesters:Renewable Linear Polyesters with High Flame Retardancy

Biobased urea nowadays attracts increasing attention as a biomass resource with giant potential,which benefits from the development of biobased ammonia and ecological sanitation system.Urea is an ideal feedstock for chemical industry and developing new urea-based polymer materials can take advantage of the urea resource.In this work,a class of renewable linear polyesters,namely polyisocyanuratoesters(PICEs)were synthesized from a urea-based monomer bis(2-carbomethoxyethyl)isocyanurate and biobased aliphatic diols.Compared with conventional aliphatic polyesters,PICEs containing isocyanurate rings in the polymer chain backbone exhibit outstanding flame retardancy that both PICE-4(the number‘4’refers to the number of methylene in diols,e.g.4 for butylene and 6 for hexylene)and PICE-6 have high limiting oxygen index values over 30%.In the UL 94 tests,PICE-6 reaches V-1 rating;while V-2 is found for PICE-10.All PICEs exhibit similar pyrolysis behavior that the temperatures of 5%weight loss are around 320°C.PICEs are found to have glass transition among 20°C-45°C.No crystallization behavior is observed without annealing except for PICE-10,which can crystallize even at room temperature.