EFFECT OF CHEMICAL STRUCTURE OF COMONOMERS ON THE PROPERTIES OF COPOLYESTERS

The effect of different kinds of comonomers with or without flexible chain on properties of copolyesters, such as transition temperature, crystallization velocity, crystallinity and size Of crystallites, is studied. The experimental results indicate the obvious difference in properties between comonomers with iso-and ortho-structure of phenyl ring and comonomers with flexible chain. The influence of chemical structure of comonomers on properties of copolyesters is discussed.

A mechanistic study of flame retardance of novel copolyester phosphorus containing linked pendant groups by TG/XPS/direct Py-MS

The flame retardant mechanism of the copolyester phosphorus containing linked pendant groups was investigated by thermogravimetric （TG）, X-ray photoelectron spectroscopy （XPS） and direct insertion probe pyrolysis mass spectrometry （DP-MS） technique. TG results show that the incorporation of phosphorus containing unit linked pendant groups can destabilize the copolyester due to the cleavage of P-CH2 bond, and phosphorus containing units cannot promote the char-formation of the copolyester during the thermal degradation of the copolyester. XPS spectra indicate that with the increase of the temperature, the P-CH2 bonds of the copolyester break down gradually, the concentration of phosphorus in the condensed phase products decrease gradually and the chemical state of phosphorus does not change in the temperature of 250-380 ℃. Direct pyrolysis MS suggests that the P-CH2 bonds cleavage occurs at pendant groups and species containing phosphorus can volatilize into the gas phase. A flame retardant mechanism is proposed for the gas phase mode of action of the halogen-free copolyester phosphorus containing linked pendant groups.

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 AVERAGE SEQUENCE LENGTH DETERMINATION OF AROMATIC-ALIPHATIC COPOLYESTERS CONTAINING POLY(ALKYLENE OXALATE)UNITS

Two series of aromatic-aliphatic random copolyesters(PEBTOXS)with diverse diol ratios have been synthesized by direct melting polycondensation.Two kinds of diols(glycol(EG)and 1,4-butanediol(BD))are used in combination in order to adjust crystallization and tensile properties,and three kinds of diacids(dimethyl terephthalate(DMT),diethyl oxalate(DEOX),and sebacic acid(SA))are involved.~1H-NMR spectra quantify both composition and structure,and show that the final contents in copolyesters appropriate to the ...

Synthesis and Structure of Butylene Terephthalate-ε-Caprolactone Copolyesters

A series of butylene terephthalate-E-caprolactone copolyesters (BCL) with different hard segment content were successfully synthesized and characterized by 1H-NMR. DSC. PLM and U viscometer, The sequence structure and crystallization characteristics of BCL copolyesters were carefully investigated.

Synthesis and Characterization of Poly(terephthalic acid-2,5-furandicarboxylic acid-1,8-octanediol) Copolyester

Terephthalic acid,2,5-furandicarboxylic acid and 1,8-octanediol were adopted as monomers and antimony trioxide as catalyst,and poly(terephthalic acid-2,5-furandicarboxylic acid-1,8-octanediol) copolyesters identified as PEOT-x,where x is the mole fraction of furandicarboxylic acid in the samples,were synthesized by direct esterification.The molecular structure of the copolyesters was characterized by FTIR and 1H NMR spectroscopy.Gel permeation chromatography (GPC),differential scanning calorimetry (DSC),and thermogravimetric analysis (TGA) were used to characterize the molecular weight,molar mass dispersity,glass transition temperature,and thermal stability of the copolyesters,respectively.The mechanical properties of the samples were also investigated.The number-average molecular weight (M_(n)) of the samples varies from 9 700-18 800 g/mol,and molar mass dispersity (■=M_(w)/M_(n)) from 2.15-3.34.The initial decomposition temperature of the copolyesters is in the 332-356 ℃ range,with maximum decomposition rates at 390-410 ℃,while the glass transition temperature (Tg) varies from 0-33 ℃.Mechanical test shows that PEOT-10 has the highest tensile strength,while PEOT-90 has the largest tensile modulus and elongation at break.The experimental results show that these copolyesters can be synthesized with relatively high molecular weights,good thermal stability,and fair mechanical properties,which makes them excellent replacements for commercial polyesters,such as PET,and these properties can be tuned through the relative amounts of biomass monomer 2,5-furandicarboxylic acid used in the reactions.

Nonisothermal Crystallization Kinetics of Poly(butylene adipate-co-terephthalate) Copolyester

Nonisothermal crystallization behavior of poly(butylene adipate-co-terephthalate)(PBAT) synthesized via direct esterification and polycondensation reactions was investigated by the differential scanning calorimetry(DSC).The Avrami equation modified by Jeziorny and the Z.S.Mo equation were employed to describe the non-isothermal crystallization kinetics of copolyester samples.The test results showed that the Avrami equation was successful in describing nonisothermal crystallization process of PBAT copolyesters.PBAT copolyester could give birth to secondary crystallization.The crystallization parameter(Zc) increased with an increasing cooling rate and the Avrami exponent(n) was around 2.3.For a given cooling rate,the value of Zc demonstrated a sagging trend with an increase in adipic acid(AA) content.The equation proposed by Z.S.Mo was successful in describing the nonisothermal crystallization kinetics of PBAT copolyesters.

Research in the Degradation and Antifouling Performance of Copolyesters of L-Lactide and ε-Caprolactonen

Block copolyesters of L-lactide and ε-caprolactone were synthesized by melt copolymerization of ε-caprolactone and L-lactide.The degradation performance of copolyesters was investigated by quartz crystal microbalance with dissipation(QCM-D).Diisocyanate terminated copolyesters could obtain via the reaction of copolyesters and diisocyanate.Diisocyanate terminated copolyesters could react with polyol resin to prepare degradable polyurethane which can be used in antifouling coatings.In this paper,we also discussed the degradation products release action and antifouling performance of the copolyesters film.

PREPARATION AND PROPERTIES OF POLY(LACTIC ACID-CO-GLYCOL TEREPHTHALIC ACID)COPOLYESTER

To obtain a kind of biodegradable polymer material with satisfactory properties, a new biodegradable copolyester poly（lactic acid-co-glycol terephthalate） （PETA）, was synthesized from three monomers of lactic acid, glycol and terephthalic acid. The resulting copolyesters, PETA, were characterized by FT-IR, ^1H-NMR, DSC, TGA and by the ways of weight loss rate to characterize their biodegradability. The findings in this work indicated that, the Tins and Tas of copolyesters PETA increased with increasing contents of the terephthalic acid units. From the biodegradation tests in natural soil, boiling water, acid buffer solution and alkali buffer solution, it was shown that the biodegradability of copolyesters PETA decreased with increasing contents of the terephthalic acid units.

PROPERTIES AND MICROSTRUCTURE OF AROMATIC LIQUID CRYSTALLINE COPOLYESTERS

The properties and structures of thermotropical liquid crystalline copolyesters based on p-hydroxybenzoic acid (PHBA), terephthalic acid (TPR) and bisphenol A (BPA) were studied by DSC, WAXD, hot stage polarized microscopy and NMR. It was found that most of the copolyesters were soluble in many common organic solvents. The copolyesters had low T-m/T-f values and a broad range of liquid crystal phase, making the polymers readily melt-processable. The effects of annealing at different temperatures on the copolyester containing 33% PHBA were also discussed. It was noted that annealing at ca. 200 degrees C (below Tc - n) could lead to the increasing of the crystallinity of the copolyester while the microstructure and sequence structure had not changed. Annealing at ca. 280 degrees C (near Tc - n) could bring a change of crystal and sequence structure and simultaneously made the microdomains be ordered more perfectly.

THE NON—ISOTHERMAL CRYSTALLIZATION KINETICS OF A LIQUID CRYSTALLINE RANDOM COPOLYESTER WITH DIFFERENT COMPOSITIONS

The non-isothermal crystallization kinetics analysis of liquid crystalline random copolyestercomposed of p-oxybenzoate (B) and 2, 6-oxynaphthoate (N) monomers was carried out by meansof differential scanning calorimetry basing on Ziabicki and Jeziorny method. Although the compo-sition of 58/42 B-N copolyester had poorer thermodynamic crystallizability comparing with thoseof 30/70 and 75/25, its kinetic crystallizability Go was slightly larger. This fact was due to thepoorer match of sequences of 58/42 B-N in domains of nematic melt,and therefore better mobilityof chains during crystallization. The Avrami exponents of three composition species were allabout 2. 5, implying two dimensional growth in so-called non-periodic layer crystallites and a mixture of homogeneous and heterogeneous nucleation.

INFLUENCE OF POLYMER CHARACTERISTICS AND MELT-SPINNING CONDITIONS ON THE PRODUCTION OF HIGH RANDOMNESS 60PHB/PET THERMOTROPIC LIQUID CRYSTAL COPOLYESTER FIBER

Six samples of linear high randomness 60PHB/ PET thermotropic liquid crystal copolyesters are made by melt copolymerization at 290℃ , whose randomness about 0.955 is measured by the discernible ’H-NMR spectrometer. High tenacity, high module fiber is prepared by melt spinning in liquid crystal phase. The effect of molecular weight, shear rate, temperature as well as spinning drawn ratio on the mechanical behavior of 60PHB / PET copolyester fiber are shown that, lower shear rate (2 10 s-1), higher temperature melting （300℃ ）, lower temperature spinning （280℃ ） and higher molecular weight are favourable to the increase of the fiber mechanical properties. With the variance of drawn ratio, fiber mechanical property has a transition point due to traversion from shear-orientation to drawn-orientation. The copolyester fiber has high crystallinity, high orientation at the crystalline region, high chain orientation and high regular fibrillar structure.

MOLECULAR CHAIN STRUCTURE AND CRYSTALLINE STRUCTURE OF PB-ET COPOLYESTER

The molecular chain structure and crystalline structure of PB-ET copolyester made by con-densation polymerization are studied by means of 13C nuclear magnetic resonance spectroscopy(13C NMR),dynamic mechanical analysis （DMA）,wide angle X-ray scattering （WAXS）,depolarized light intensity （DLI） and stress-strain measurement（S-S）.It is shown that PB-ETcopolyester is a random copolymer.Because of different ratios of EG（ethylene glycol）to BD（butane diol）in the copolyester,its crystalline forms and mechanical properties vary remarkably.With the increasing amount of BD,its crystallization kinetic parameters n,k and t1/2-1 increaserapidly.When EG/BD equals 25/75 （mole ratio）,the copolyester has αβ transition as PBTdoes.

SYNTHESIS AND CHARACTERIZATION OF THERMOTROPIC COPOLYESTERS AND COPOLY (ESTER-AMIDE)S CONTAINING OXYETHYLENE-ETHER AS THE SPACER

Flexible oxyethylene-ether was introduced into the aromatic copolyesters and copoly (ester-amide)s to reduce the melting point of resulting polymers. The melting point was greatly reduced to 200 degrees C or even lower in some cases, and the molecular weight was satisfactorily high as reflected by inherent viscosity. The polymers exhibited high thermal stability and good mechanical properties as determined by TGA and mechanical tests. The copolyester showed better crystallinity and liquid crystallinity than corresponding copoly (ester-amide)s with similar monomer composition as reflected by POM observation and WAXD study. The melting points for both copolyesters and copoly (ester-amide)s showed great dependence on the p-acetoxybenzoic acid (PAB) content in monomer composition and reached the lowest value when PAB was 29 mol%.

STUDY ON THE PHASE TRANSITION KINETICS OF THERMOTROPIC LIQUID CRYSTALLINE AROMATIC-ALIPHATIC COPOLYESTER

The phase transition kinetics of thennotropic liquid crystalline aromatic-aliphatic regular copolyester: were studied by DSC. By means of Kissinger's method the kinetic equation and parameters including activation energy, rate order and preexponential factor for phase transition from nematic to isotropic were obtained. The activation energy from crystal to nematic was also presented.

DYNAMIC RHEOLOGICAL AND THERMAL PROPERTY OF Q-RESIN CONTAINING THERMOTROPIC LIQUID CRYSTALLINE COPOLYESTER AND ITS BLEND WITH PET

A thermotropic liquid crystalline copolyester (LCP) based on p-acetoxy-benzoic acid (49.9mol%), 2,7-diacetoxynaphthalene (22.3 mol%), terephthalic acid (22.3%) and Q-resin (polyethylene 2,6-naphthalene, 5.5%) was prepared via melt transesterification, and then a blend was prepared by physically mixing 40% therm0tropic liquid crystallline copolyester and 60% polyethlene terephthalate (PET). The thermal properties of both-4he LCP and the blend were studied by DSC and the result showed that the various transition temperatures for the blend were rather close to those for pure PET. The thermal stability of LCP, blend and PET was characterized by TGA. The dynamic theological properties of LCP and thc blend were studied by the oscillation test on a rheometric mechanical spectrometer( Instron RM3250) with parallel plate disk. The results showed that the theological behavious of the blend melt exhibit as conventional polymeric melt in the whole experimental frequency range (0.02—12 Hz). However, for the melt

PRIMARY STUDY ON BLENDS BASED ON THERMOTROPIC LIQUID CRYSTAL COPOLYESTER AND PET

The blend system composed of PET and thermotropic liquid crystal copolyester based on hydroxy benzoic acid, terephthalic acid, diacetylnaphthalene and PET was studied. The results indicated that LCP could play the role of crystal nuclei. The introduction of LCP decreased the melt viscosity of the system and fibrillous structure could be formed in favor conditions.

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.

TRANSESTERIFICATION OF POLY(BISPHENOL A CARBONATE) WITH AROMATIC AND ALIPHATIC SEGMENTS IN BUTYLENE TEREPHTHALATE-CAPROLACTONE COPOLYESTER

In this article, the transesterification of poly(bisphenol A carbonate) (PC) with butylene terephthalate-caprolactone copolyester at a weight ratio 50/50 (BCL(21)) was thoroughly investigated by proton nuclear magnetic resonance spectroscopy ('H-NMR), in conjunction with a model compound. The 1 H-NMR results of the annealed blend PC/BCL(21) show that the formation of bisphenol A-terephthalate ester units is the same as in the annealed blend of PC with PBT, and the transesterification actually occurs between PC and butylene terephthalate (BT) segments in BCL(21). By comparison with the model compound bisphenol A dibutyrate, the new signal appearing at δ= 2.56 in the 1H-NMR spectrum confirms the existence of bisphenol A caprolactone ester units resulting from the exchange reaction of PC with caprolactone (CL) segments. 1H-NMR analysis of the transesterification rates reveals that the reaction of PC with aromatic and aliphatic segments in BCL(21) proceeds in a random manner. The miscibility of the blend PC/BCL(21) copolyester is favorable for the transesterification of PC with BT segments and CL segments.

OPTICALLY ACTIVE COPOLYESTERS BASED ON AXIALLY DISSYMMETRIC 1,1’-BINAPHTHALENE-2,2’-DIYL UNITS

Optically active copolyesters based on axially dissymmetric 1,1'-binaphthalene-2,2'-diyl units have been preparedand characterized by specific rotation, ^(13)C-NMR and CD spectra. The results show that the rotation signs of tribasiccopolyesters or the mixture of corresponding homopolyesters obey a three dimensional quadrant pattern. The composition ofthe copolyesters was determined from ^(13)C-NMR spectra to be triad sequence distributions and corresponding with the ratioby feed.