Co[poly(ethylene terephthalate-p-oxybenzoate)] thermotropic copolyester. II. X-ray diffraction analysis

A series of co[poly(ethylene terephthalate-p-oxybenzoate)] thermotropic copolyester with different compositions were prepared by the copolymerization of either poly(ethylene terephthalate) (PET) polymer or its oligomer with p-acetoxy-benzoic acid. The polymeric products were subjected to solid-state polymerization for various time intervals. Effects of composition ratio and solid-state polymerization time on X-ray diffraction behavior were investigated. It is found that the effect of transesterification induced by solid-state polymerization causes an increase in crystallinity with the copolyesters having high mol % of p-oxybenzoic acid (POB) moiety and causes a decrease in crystallinity with the copolyesters having high mol % of PET moiety. In general, the crystallinity of copolyesters is first increased and then decreased as solid-state polymerization time proceeds. However, the crystallinity of copolyester having POB/PET = 80/20 composition is increased generally at 4-h solid-state polymerization. It is also found that the crystallinity of copolyesters is decreased by quenching. The copolyester based upon either PET oligomer with 4-h solid-state polymerization or PET polymer with 8-h solid-state polymerization shows the most similar X-ray diffraction pattern with that of Eastman 10109. © 1993 John Wiley & Sons, Inc.     

Studies on co[poly(ethylene terephthalate-p-oxybenzoate)] thermotropic copolyester: Thermomechanical and thermodynamic properties

A series of co[poly(ethylene terephthalate-p-oxybenzoate)] thermotropic copolyesters were prepared by the copolymerization of poly(ethylene terephthalate) (PET) as moiety (II) and p-acetoxybenzoic acid (POB) as moiety (I). The polymeric products obtained were subjected to solid-state polymerization. Characterization of the copolyesters by thermomechanical analysis shows that properties such as the coefficient of thermal expansion, transition temperature, and maximum softening rate temperature varied directly as a function of composition as well as did solid-state polymerization time. All thermomechanical data were found to increase with the solid-state polymerization time due to the increase in the degree of polymerization and the effect of annealing. The coefficient of thermal expansion behaves in a manner that is interpretable by the crystalline state of the copolyester. The relationship between the free-volume fraction and thermodynamic properties is further correlated for a more comprehensive discussion on its molecular arrangements. © 1995 John Wiley & Sons, Inc.     

Studies on co[poly(ethylene terephthalate-p-oxybenzoate)] thermotropic copolyester (I): Synthesis and thermogravimetric behavior

A series of co[poly(ethylene terephthalate-p-oxybenzoate)] thermotropic copolyester was synthesized from various ratios of two different moieties of either poly(ethylene terephthalate) (PET) or its oligomer as moiety ( II ) with p-acetoxybenzoic acid as moiety ( I ) through the polycondensation process. The polymeric products obtained were then ground and subjected to solid-state polymerization under vacuum for various polymerization times. Thermogravimetric analysis (TGA) and the derivative thermogravimetric analysis (DTG) were performed with these samples obtained. Also, a commercial product, Eastman 10109, was analyzed in comparison with these samples. It was found that the copolyesters made of PET and of its oligomer in a p-oxybenzoate (POB):PET = 80 : 20 composition ratio and subjected to 8 and 4 h solid-state polymerization times, respectively, showed the most similar thermogravimetric behavior with Eastman 10109. © 1993 John Wiley & Sons, Inc.     

Study on co[poly(butylene terephthalate‐p‐oxybenzoate)] thermotropic copolyester. II. Thermal behavior and crystalline morphology

The POB/PBT copolyesters, designated B28, B46, B64, and B82, were prepared from p‐acetoxybenzoic acid (PAB) and poly(butylene terephthalate) (PBT). The polymeric products obtained were then ground and subjected to solid‐state polymerization under vaccum for 4 h. The melting and crystallization behaviors of these copolyesters haven been studied by differential scanning calorimetry (DSC). In the DSC scan of the POB‐rich composition, the endothermic peak shows obscurely, and enthalpy of fussion becomes small due to the change in the crystalline morphology from isotropic to anisotropic. In general, the melting point of the copolyester is increased by the solid‐state polymerization reaction. Also, thermogravimetric analysis (TGA) were performed with these samples obtained. It was found that the decomposition temperature (T_d ) is increased as the POB content is increased. Effects of composition and solid‐state polymerization on the decomposition temperature of copolyesters are also discussed. The crystalline morphology of copolyester was investigated with a Zeiss polarized optical microscope. It was found that the POB/PBT copolyesters with 60 mol % POB was shown to be highly anisotropic. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2363–2368, 2000     

Blends of poly(ethylene terephthalate) with co[poly(ethylene terephthalate-p-oxybenzoate)]. II. Composition effect on the rate of crystallization

Poly(ethylene terephthalate) (PET) was blended with four different kinds of co[poly(ethylene terephthalate-p-oxybenzoate)] copolyesters, designated P28, P46, P64, and P82, with the level of copolyester varing from 1 to 15 wt %. All samples were prepared by melt-mixing in a Brabender Plasticorder for 8 min. The crystallization behavior of samples were then studied via DSC. The results indicate that these four copolyesters accelerate the crystallization rate of PET in a manner similar to that of a nucleating agent. The acceleration of the PET crystallization rate was most pronounced in the PET/P28 blends with a maximum level at 10 wt % of P28, and in the PET/P28 blends, at 5 wt % of P82. The melting endotherm onset temperatures and the melting peak widths for the blends are comparable with those of neat PET. These results imply that the stability of PET crystalline phase in the blends does not change by blending. The observed changes in crystallization behavior, however, are explained by the effect of the physical state of the copolyester during PET crystallization as well as the content of the p-oxybenzoate (POB) moiety in corporated into the blends. © 1995 John Wiley & Sons, Inc.     

Co[poly(ethylene terephthalate-p-oxybenzoate)] and its blends with poly(ethylene terephthalate): Transesterification reaction and fractured surface morphology

A series of co[poly(ethylene terephthalate-p-oxybenzoate)] copolyesters, viz., P28, P46, P64, and P82, were synthesized. These copolyesters were blended with poly(ethylene terephthalate) (PET) at the level of 10 wt % at 293°C for different times. The results from proton NMR analysis reveal that a significant amount of the transesterification has been detected in the cases of PET/P28, PET/P46, and PET/P64 blends. The blending time necessary before any transesterification reaction could be detected depends on the composition of copolyester, e.g., a time less than 3 min is needed for both PET/P28 and PET/P46 blends, while a longer time of 8–20 min is needed for the PET/P64 blend. It is concluded that the higher the mol ratio of the POB moiety in the copolyester is the longer the blending time needed to initiate the transesterification. The degree of transesterification is also increased as the duration of melt blending is prolonged. Two-phase morphology was observed by scanning electron microscopy (SEM) micrographs in all the blends. It was observed that the more similar the composition between the copolyester and PET in the blends is the better the miscibility or interfacial adhesion between the two phases. Moreover, the miscibility can be markedly improved by the duration of melt blending. © 1996 John Wiley & Sons, Inc.     

支化聚酯的合成及热性能研究

通过直接酯化-缩聚工艺,在聚对苯二甲酸乙二醇酯(PET)聚合的缩聚过程中分别引入第三组分——3-羟甲基丙烷(TMP)、季戊四醇(PER)或双季戊四醇(DPT)合成了一系列不同的支化PET,并采用氢核磁共振波谱仪(1H-NMR)、差示扫描量热仪(DSC)和热重分析(TG)表征了产物的结构和性能。结果表明:与纯PET相比,经TMP、PER或DPT改性后的支化PET的玻璃化转变温度(Tg)均下降,含摩尔分数0.3%DPT改性的支化PET的Tg最低;除TMP1-PET外,各支化PET的冷结晶温度(Tc)都增大;各支化PET的熔点(Tm)也都呈现下降趋势;除PER3-PET外,各支化PET的结晶焓ΔHc都有所下降,而各支化PET的熔融焓ΔHm却变化不大;所得到的各支化PET具有较好的热稳定性能。     

Synthesis and characterization of poly(L‐lactic acid)‐b‐poly(ethylene terephthalate‐co‐sebacate)‐b‐poly(L‐lactic acid) copolyesters

Random copolyester namely, poly(ethylene terephthalate‐co‐sebacate) (PETS), with relatively lower molecular weight was first synthesized, and then it was used as a macromonomer to initiate ring‐opening polymerization of l ‐lactide. ¹H NMR quantified composition and structure of triblock copolyesters [poly(l ‐lactic acid)‐b‐poly(ethylene terephthalate‐co‐sebacate)‐b‐poly(l ‐lactic acid)] (PLLA‐PETS‐PLLA). Molecular weights of copolyesters were also estimated from NMR spectra, and confirmed by GPC. Copolyesters exhibited different solubilities according to the actual content of PLLA units in the main chain. Copolymerization effected melting behaviors significantly because of the incorporation of PETS and PLLA blocks. Crystalline morphology showed a special pattern for specimen with certain composition. It was obvious that copolyesters with more content of aromatic units of PET exhibited increased values in both of stress and modulus in tensile test. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Thermoplastic elastomers derived from bio‐based monomers

Series of copolyesters based on poly(propylene succinate) (PPS) and poly(butylene succinate) (PBS), which can be produced from biological feedstock, and postconsumer poly(ethylene terephthalate) (PET) were synthesized with the aim of developing sustainable materials, which combine the mechanical properties of high performance elastomers with those of flexible plastics. The aliphatic polyesters were synthesized by the catalyzed two‐step transesterification reaction of dimethyl succinate, 1,3‐propanediol, and 1,4‐butanediol followed by melt reaction with PET in bulk. The content of PET segments in the polymer chains was varied from about 10 to 100 wt % per 100 wt % PPS or PBS. The effect of the introduction of the PET segments on the structure, thermal, physical, and mechanical properties was investigated. The composition and structure of these aliphatic/aromatic copolyesters were determined by NMR spectroscopy. The thermal properties were investigated using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The level of crystallinity was studied by means of DSC and wide‐angle X‐ray scattering. A depression of melting temperature and a reduction of crystallinity of copolyesters with increasing content of PET segments were observed. Consequently, the tensile modulus and strength of copolyesters decreased, and the elongation at break increased with PET content in the range of 10?50 wt %. Thus, depending on PET content, the properties of copolyesters can be tuned ranging from semicrystalline polymers possessing good tensile modulus (380 MPa) and strength (24 MPa) to nearly amorphous polymer of high elongation (～800%), and therefore they may find applications in thermoplastics as well as elastomers or impact modifiers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39815.     

Preparation and biodegradation of copolyesters based on poly(ethylene terephthalate) and poly(ethylene glycol)/oligo(lactic acid) by transesterification

The poly(ethylene terephthalate‐co‐ethyleneoxide‐co‐DL ‐lactide) copolymers were successfully prepared by the melt reaction between poly(ethylene terephthalate), poly(ethylene glycol), and DL ‐oligo(lactic acid) without any catalysts. The transesterification between ethylene terephthalate, ethyleneoxide, and lactide segments during the reaction was confirmed by the ¹H NMR analysis. The effect of reaction temperatures and the starting feed ratios on the molecular microstructures, molecular weights, solubility, thermal properties, and degradability of the copolyesters was extensively studied. The values of crystallization temperature, melting temperature, crystallization, and melting enthalpy of the copolyesters were found to be influenced by the reaction temperatures, starting feed ratios, etc. The copolyesters showed good tensile properties and were found to degrade in the soil burial experiments during the period of 3 months. The morphology of the copolyester films were also investigated by scanning electron microscopy during soil burial degradation. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Crystallization of 2‐methyl‐1,3‐propanediol substituted poly(ethylene terephthalate). I. Thermal behavior and isothermal crystallization

Differential scanning calorimetry (DSC) was used to evaluate the thermal behavior and isothermal crystallization kinetics of poly(ethylene terephthalate) (PET) copolymers containing 2‐methyl‐1,3‐propanediol as a comonomer unit. The addition of comonomer reduces the melting temperature and decreases the range between the glass transition and melting point. The rate of crystallization is also decreased with the addition of this comonomer. In this case it appears that the more flexible glycol group does not significantly increase crystallization rates by promoting chain folding during crystallization, as has been suggested for some other glycol‐modified PET copolyesters. The melting behavior following isothermal crystallization was examined using a Hoffman–Weeks approach, showing very good linearity for all copolymers tested, and predicted an equilibrium melting temperature (T_m⁰) of 280.0°C for PET homopolymer, in agreement with literature values. The remaining copolymers showed a marked decrease in T_m⁰ with increasing copolymer composition. The results of this study support the claim that these comonomers are excluded from the polymer crystal during growth. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2592–2603, 2006     

Study on the kinetics of transesterification reaction between poly(ethylene terephthalate) and its copolyesters

Polyethylene terephthalate (PET) was blended with two kinds of co[poly(ethylene terephthalate-p-oxybenzoate)] (POB–PET) copolyester, designated as P46 and P64, respectively. The PET and POB–PET copolyester were combined in the ratios of 85/15, 70/30, and 50/50. The blends were melt mixed in a Brabender Plasticorder at 275, 285, and 293°C for different amounts of time. The transesterification reactions during the melt mixing processes of PET with POB–PET copolyester blends were detected by proton nuclear magnetic resonance analysis. The values of the rate constants are a function of temperature and the composition of blends. The transesterification reactions that may occur during the melt mixing processes have been discussed also. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2727–2732, 1999     

Synthesis and properties of poly(alkylene p,p′-bibenzoate-co-adipate)s

Various poly(alkylene p,p′-bibenzoate-co-adipate)s were prepared by melt polycondensation of dimethyl-p,p′-bibenzoate, adipic acid, and an alkylene glycol. The copolyesters were characterized by inherent viscosity, FTIR, proton NMR, DSC, polarized microscopy, and X-ray diffraction. The polymer composition and sequence distribution of the copolyesters can be seen from NMR spectra. The copolyesters exhibit a degree of randomness of about 1, indicating that they are random copolymers. From the DSC data, the glass transition temperature (T_g) and melting point (T_m) of the copolyesters can be detected. When the content of the flexible adipate unit increases, the T_g of copolyesters decreases significantly. The type of alkylene glycol used also affects the T_g to some extent. The copolymerization effect decreases crystallinity and the T_m of the copolyesters. The DSC, polarized microscopy, and X-ray diffraction data show that some copolyesters derived from 1,6-hexanediol exhibit a monotropic smectic phase. As the molar fraction of adipate unit in diacid units, x, is more than 0.4, the liquid crystallinity is completely destroyed. © 1997 John Wiley & Sons, Inc. J Appl Polm Sci 65:893–900, 1997     

Structure–property relationship of poly(cyclohexane 1,4-dimethylene terephthalate) modified with high trans-1,4-cyclohexanedimethanol and 2,6-naphthalene dicarboxylicacid

A series of novel poly(1,4-cyclohexanedimthylene terephthalate-co-1,4-cyclohxylenedimethylene 2,6-naphthalenedicarboxylate) (PCTN) copolyesters were successfully melt polymerized using different content of trans- or cis-isomers. Before evaluations, the performance properties, their actual chemical composition, chemical structure, and molecular weight were determined using proton nuclear magnetic resonance (¹H-NMR), Fourier transform infrared spectroscopy (FTIR), and intrinsic viscosity (IV) measurements. Thermal studies of obtained copolyesters were carried out using differential scanning calorimetry (DSC). Thermal degradation behaviors were analyzed by thermogravimetric analysis (TGA). Randomly oriented film specimens were developed using a hot-press and their thermal, barrier, dimensional stability, and optical properties were analyzed and compared with conventional poly(ethylene terephthalate) (PET) and poly(ethylene naphthalate) (PEN). The results revealed that glass transition temperature (T_g), melting temperature (T_m), and crystallinity (X_c) of the synthesized copolyesters are increased in a linear trend by increasing the trans-1,4-cyclohexanedimethanol (trans-CHDM) isomers. It was also found that synthesized films had better thermal, barrier, optical, and dimensional stability properties than conventional PET and PEN films. Results clearly indicated that high trans-CHDM isomers significantly improve the performance properties of the fabricated films. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48950.     

Morphological consequences of interchange reactions during solid state copolymerization in poly(ethylene terephthalate) and polycarbonate oligomers

Poly(ethylene terephthalate) (PET) (IV:0.15 dL/g) oligomer was obtained by depolymerisation of high molecular weight PET. Polycarbonate (PC) oligomer (IV: 0.15 dL/g) was synthesized by standard melt polymerization procedure using bisphenol A and diphenyl carbonate in the presence of a basic catalyst. Blends of varying compositions were prepared by melt blending the chemically distinct PET and PC oligomers. The copolymer, poly(ethylene terephthalate-co-bisphenol A carbonate) was synthesized by simultaneous solid state polymerization and ester-carbonate interchange reaction between the oligomers of PET and PC. The reaction was carried out under reduced pressure at temperatures below the melting temperature of the blend samples. DSC and WAXS techniques characterized the structure and morphology of the blends, while ¹NMR spectroscopy was used to monitor the progress of interchange reactions between the oligomers. The studies have indicated the amorphisation of the PET and PC crystalline phases in solid state with the progress of solid-state polymerization and interchange reaction.     

Blends of poly(butylene terephthalate) with co[poly(ethylene terephthalate-p-oxybenzoate)]: Crystallization behaviors

Polyblends of poly(butylene terephthalate) (PBT) with four different types of co[poly(ethylene terephthalate-p-oxybenzoate)] copolyester, designated as P28, P46, P64, and P82, were prepared by melt-blending. The crystallization behaviors of the blends were then studied by differential scanning calorimetry and polarized optical microscopy (POM). Crystallization rate and temperature of neat PBT are increased when less than 10 wt% of P28 is blended. On the contrary, crystallization rate and temperature of neat PBT decrease when 10 wt% of P46, P64, or P82 copolyesters is blended. The crystallization behaviors of the blends are confirmed by the POM observations at the cooling cycles of the melts. On the other hand, melting endotherm onset temperature and melting peak width for all blends are comparable with those of neat PBT. These results imply that the stability and distribution of PBT crystallites in the blends are not significantly influenced by blending. The effects of POB content in the composition of the blends on the crystalline morphology were also presented. It is found that the structure of crystallites of the blends changed gradually with increasing the POB content in the composition of copolyester from lamellar to cross-like spherulite structures. © 1996 John Wiley & Sons, Inc.     

Poly(ethylene terephthalate‐co‐isophthalate) copolyesters obtained from ethylene terephthalate and isophthalate oligomers

A series of poly(ethylene terephthalate‐co‐isophthalate) copolyesters containing upto 50%‐mole of isophthalic units were prepared by polycondensation from ethylene terephthalate and ethylene isophthalate fractions of linear oligomers containing from 5 to 6 repeating units in average. The polyesters were obtained in good yields and with high‐molecular‐weights. The microstructure of the copolyesters was studied as a function of reaction time by ¹³C‐NMR showing that a random distribution of the comonomers was achieved since the earlier stages of polycondensation. The melting temperature and enthalpy of the copolyesters decreased with the content of isophthalic units so that copolyesters containing more than 25% of these units were amorphous. Isothermal crystallization studies made on crystalline copolyesters revealed that the crystallization rate of copolyesters decreased with the content in isophthalic units. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of monomer composition on the rheological properties of poly(p-oxybenzoate-co-ethylene terephthalate)s

Summary Effect of monomer composition on the dynamic viscoelastic properties and the steady flow properties of thermotropic liquid crystalline poly (p-oxybenzoate-co-ethylene terephthalate)s in the fluid state have been investigated as compared with the isotropic melt of the copolyester including 28 mol% p-oxybenzoate unit (POB). The liquid crystalline copolyesters show the rheological transition temperature, which increases with increasing the content of POB unit. Above the transition temperature, all the thermotropic copolyesters exhibit much higher compliance and much more shear-thinning behavior of the apparent viscosity than the isotropic melt of the non-liquid crystalline copolyester.     

Preparation and properties of poly(ethylene terephthalate)/ATO nanocomposites

Antimony doped tin oxide (ATO) nanoparticles modified poly(ethylene terephthalate) (PET) composites used for manufacturing antistatic PET fiber were synthesized by in situ polymerization. The crystallization and multiple melting behavior of the nanocomposites were systemically investigated by means of Differential Scanning Calorimeter (DSC), Fourier Transform Infrared (FTIR), X‐ray Diffraction (XRD) techniques. The degree of crystallinity in nanocomposites increased with increasing ATO content. Smaller and more incomplete crystals are presented in the crystalline regions of the nanocomposites with increasing the content of ATO, which could be attributed to heterogeneous nucleation effects of ATO nanoparticles. Dynamic Mechanical Analysis (DMA) measurements showed that the storage moduli of the nanocomposites increased with increasing the content of ATO, due to formation of immobilized layer between polymer and filler. The interactions between ATO and PET molecules result in high tan δ for the PET/ATO nanocomposites. Percolation threshold of PET/ATO hybrid fibers prepared by the nanocomposites at room temperature was as low as 1.05 wt %, much lower than that of the composites filled with conventional conductive particles. Adding ATO nanoparticles obviously improves the conductivity of PET. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007