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     

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.     

The crystallization rate of poly(ethylene terephthalate) accelerated by co[poly(butylene terephthalate‐p‐oxybenzoate)] copolyesters

Poly(ethylene terephthalate) (PET) was blended with three different kinds of co[poly(butylene terephthalate‐p‐oxybenzoate)] copolyesters, designated B28, B46, and B64, with the level of copolyester varying from 1 to 15 wt %. All samples were prepared by solution blending in a 60/40 by weight phenol/tetrachloroethane solvent at 50°C. The crystallization behavior of samples was then studied via differential scanning calorimetry. The results indicate that these three copolyesters accelerate the crystallization rate of PET in a manner similar to that of a nucleating agent. The acceleration of PET crystallization rate was most pronounced in the PET/B28 blends with a maximum level at 10 wt % of B28. The melting temperatures for the blends are comparable with that of pure PET. The observed changes in crystallization behavior are explained by the effect of the physical state of the copolyester during PET crystallization as well as the amount of copolyester in the blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 587–593, 2000     

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.     

Interchange reactions between poly(ethylene terephthalate) and its copolyesters

Poly(ethylene terephthalate) (PET) was blended with two kinds of co[poly-(ethylene terephthalate-p-oxybenzoate)] (POB-PET) copolyester, designated P46 and P64. 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 times. The interchange reactions detected by proton nuclear magnetic resonance analysis occur during the processing at a greater level if the blending time increases. The interchange reactions are as a function of temperature, blending times, and composition of blends. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1591–1595, 1998     

Characterizations for blends of phosphorus-containing copolyester with poly(ethylene terephthalate)

High molecular weight phosphorus-containing copolyesters, poly(ethylene terephthalate)-co-poly(ethylene DDP) (PET-co-PEDDP)s, were prepared and characterized with the objective of producing a non-halogen flame retardant system for practical applications. The phosphorus-containing copolyester with 30 wt% phosphorus (P30 copolyester) was blended with PET to evaluate their characteristics and flame retardancy. Higher phosphorus content results in lower crystallinity and higher char formation after thermal degradation. The rheological behavior remains similar to that of PET. The P30/PET blend possesses higher crystallization rate than the corresponding phosphorus-containing copolyester containing equal phosphorus content. Thermal and rheological behaviors of P30/PET blends are similar to PET or the phosphorus-containing copolyesters. The P30/PET blends are miscible or compatible base on single T_gs detected by DSC or DMA. The SEM/EDX phosphorus mapping image of the P30/PET blend shows uniform distribution of the phosphorus moieties within the P30/PET matrix, another indication of a compatible or miscible blend between the phosphorus-containing copolyester P30 and PET. Flame retardancy of the P30/PET blend is identical to that of the phosphorus-containing copolyester with identical phosphorus content. Blending of high phosphorus content copolyester with virgin PET provides a feasible method to obtain a flame resistant PET with LOI greater than 28.     

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.     

Recycling poly(ethylene terephtalate) wastes: Properties of poly(ethylene terephtalate)/polycarbonate blends and the effect of a transesterification catalyst

The article addresses the issue of recycling of poly(ethylene terephtalate) (PET) by melt blending with polycarbonate (PC). PET/PC blends containing various amounts of the immiscible polymers were prepared in a twin‐screw extruder. Selected compositions were also prepared in the presence of an Sn‐based catalyst to assess the influence of transesterification during melt mixing. The degree of miscibility in the blends was studied using differential scanning calorimetry, scanning electron microscopy, and mechanical testing. PET/PC blends exhibit enhanced tensile properties in comparison to neat components for compositions of PET higher than 50% and these properties are improved by the addition of a transesterification catalyst. The PET/PC blend containing 20 wt% of PC, prepared with stannous octoate, shows the smallest size of the dispersed phase because of transesterification reactions that generate copolymer molecules at the interface between the immiscible polymers. The melting temperature of PET is decreased with the increase of the PC content in blends extruded in the presence of the catalyst. Also, the temperatures of the cold crystallization of PET are higher than those of similar blends without added catalyst. Both features give rise to better molding properties because of a shortening of the cooling time in the range of 50–90 wt% of PET. POLYM. ENG. SCI. 46:1378–1386, 2006. © 2006 Society of Plastics Engineers     

Transesterification reaction kinetics of poly(ethylene terephthalate/poly(ethylene 2,6‐naphthalate) blends

The transesterification reaction of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) blends during melt‐mixing was studied as a function of blending temperature, blending time, blend composition, processing equipment, and different grades of poly(ethylene terephthalate) and poly(ethylene 2,6‐naphthalate). Results show that the major factors controlling the reaction are the temperature and time of blending. Efficiency of mixing also plays an important role in transesterification. The reaction kinetics can be modeled using a second‐order direct ester–ester interchange reaction. The rate constant (k) was found to have a minimum value at an intermediate PEN content and the activation energy of the rate constant was calculated to be 140 kJ/mol. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2422–2436, 2001     

Thermal and crystallization characteristics of poly(ethylene terephthalate) with poly(oxybenzoate‐p‐trimethylene terephthalate) copolymer

Poly(ethylene terephthalate) (PET) was blended with two different poly(oxybenzoate‐p‐trimethylene terephthalate) copolymers, designated T28 and T64, with the level of copolymer varying from 1 to 15 wt %. All samples were prepared by solution blending in a 60/40 (by weight) phenol/tetrachloroethane solvent at 50°C. The crystallization behavior of the samples was studied by DSC. The results indicate that both T28 and T64 accelerated the crystallization rate of PET in a manner similar to that of a nucleating agent. The acceleration of PET crystallization rate was most pronounced in the PET/T64 blends with a maximum level at 5 wt % of T64. The melting temperatures for the blends are comparable to that of pure PET. The observed changes in crystallization behavior are explained by the effect of the physical state of the copolyester during PET crystallization as well as the amount of copolymer in the blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1599–1606, 2002     

Microstructure and crystallization of melt‐mixed poly(ethylene terephthalate)/poly(ethylene isophthalate) blends

Physical blends of poly(ethylene terephthalate) (PET) and poly(ethylene isophthalate) (PEI), abbreviated PET/PEI (80/20) blends, and of PET and a random poly(ethylene terephthalate‐co‐isophthalate) copolymer containing 40% ethylene isophthalate (PET₆₀I₄₀), abbreviated PET/PET₆₀I₄₀ (50/50) blends, were melt‐mixed at 270°C for different reactive blending times to give a series of copolymers containing 20 mol % of ethylene isophthalic units with different degrees of randomness. ¹³C‐NMR spectroscopy precisely determined the microstructure of the blends. The thermal and mechanical properties of the blends were evaluated by DSC and tensile assays, and the obtained results were compared with those obtained for PET and a statistically random PETI copolymer with the same composition. The microstructure of the blends gradually changed from a physical blend into a block copolymer, and finally into a random copolymer with the advance of transreaction time. The melting temperature and enthalpy of the blends decreased with the progress of melt‐mixing. Isothermal crystallization studies carried out on molten samples revealed the same trend for the crystallization rate. The effect of reaction time on crystallizability was more pronounced in the case of the PET/PET₆₀I₄₀ (50/50) blends. The Young's modulus of the melt‐mixed blends was comparable to that of PET, whereas the maximum tensile stress decreased with respect to that of PET. All blend samples showed a noticeable brittleness. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3076–3086, 2003     

Primary structure and physical properties of poly(ethylene terephthalate)/poly(ethylene naphthalate) resin blends

The morphology and properties of blends of poly(ethylene naphthalate) (PEN) and poly(ethylene terephthalate) (PET) that were injection molded under various conditions were studied. Under injection molding conditions that make it possible to secure transparency, blends did not show clear crystallinity at blending ratios of more than 20 mol% in spite of the fact that crystallinity can be observed in the range of PEN content up to 30 mol%. Because both transparency and crystallinity could be secured with a PEN 12 mol% blend, this material was used in injection molding experiments with various injection molding cycles. Whitening occurred with a cycle of 20 sec, and transparency was obtained at 30 sec or more. This was attributed to the fact that transesterification between PET and PEN exceeded 5 mol% and phase solubility (compatibility) between the PET and PEN increased when the injection molding time was 30 sec or longer. However, when the transesterification content exceeded 8 mol%, molecularly oriented crystallization did not occur, even under stretching, and consequently, it was not possible to increase the strength of the material by stretching. PET/PEN blend resins are more easily crystallized by stretch heat‐setting than are PET/PEN copolymer resins. It was understood that this is because residual PET, which has not undergone transesterification, contributes to crystallization. However, because transesterification reduces crystallinity, the heat‐set density of blends did not increase as significantly as that of pure PET, even in high temperature heat‐setting. Gas permeability showed the same tendency as density. Namely, pure PET showed a substantial decrease in oxygen transmission after high temperature heat‐setting, but the decrease in gas permeability in the blend material was small at heat‐set temperatures of 140°C and higher.     

Reactive blending of poly(ethylene terephthalate)(pet)/ poly(ethylene 2,6‐naphthalate)(pen). I: Effect of mixing conditions on chain structure

Reactive blending of poly(ethylene terephthalate)/poly(ethylene naphthalene 2,6dicarboxylate) with addition of 2,2'‐bis(1,3‐oxazoline) (BOZ) has been studied under various mixing conditions for the different compositions. The transesterification level, the sequence length of both PET and PEN short blocks, and the degree of randomness were estimated using¹H NMR. The results indicate that both mixing time and temperature are the primary factors controlling the transesterification, while the chain extender BOZ can significantly accelerate the transesterification between PET and PEN at 275°C. The composition also, to some extent, influences the transerification level as the mixing time is increased. As a consequence of transesterification proceeding, the sequence structures of the reactive blends are also markedly changed, which corresponds to a transfer from an initial block structure to a multiblock structure with higher randomness. The change in the microstructure of the reactive blends has also been analyzed by a Bernoullian statistics model. The effect of the BOZ on the intrinsic viscosity of the reactive blends is discussed.     

Segmented liquid crystalline copolyesters and blending with poly(ethylene terephthalate)

Summary A series of segmented copolyesters with semi-regular structure was synthesized. In these copolymers, fully aromatic triad hard segments-HB-T-HB-, acting as mesogenic units, are linked each other by poly(ethylene terephthalate) (PET) segments with different average chain lengths as flexible spacers. The liquid crystallinity of the copolymers, i.e. the meso-phase forming ability, was studied against length of the spacer. In subsequent blending of these copolymers with PET matrix, results were compared with those from a commercial TLCP of PHB/PET random copolyester. Better mechanical properties were gained as expected since the compatibility of the segmented liquid crystalline copolyesters with the matrix is believed to be improved.     

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     

Structure and mechanical properties of compatibilized poly(ethylene terephthalate)/poly(ethylene octene) blends

Poly(ethylene terephthalate) (PET) based blends were obtained by melt blending PET with up to 30 wt% poly(ethylene‐octene) either modified with maleic anhydride (mLLDPE) or not (LLDPE). Both PET/LLDPE and PET/mLLDPE blends were immiscible. The dispersed phase particle size was large in LLDPE blends, but upon mLLDPE addition, it decreased to a small (submicron) and rather constant value with composition. This indicated compatibilization, and was attributed to specific interactions between the ester and maleic groups of PET and mLLDPE, respectively, rather than grafting reactions between components. Linear decreases in Young's modulus and yield stress, and ductility increases were observed in blends with mLLDPE. Super‐toughness was achieved in blends with mLLDPE, which took place when the critical interparticle distance (ID_c) was below 0.17 μm and with only half the cross section of the specimens broken. The ID_c of these blends and those of other blends from bibliography were compared with the adhesion levels estimated from the expected main interactions between the components of the blends. This comparison strongly indicated that, at least through an adhesion range, ID_c depends on the adhesion level, and that ID_c decreases as the adhesion level increases. POLYM. ENG. SCI. 46:172–180, 2006. © 2005 Society of Plastics Engineers     

Rheological and thermal properties of blends of modified poly(ethylene terephthalate) with p‐acetoxybenzoic acid and poly(butylene terephthalate)

Blending of thermotropic liquid crystalline polyesters (LCPs) with conventional polymers could result in materials that can be used as an alternative for short fiber‐reinforced thermoplastic composites, because of their low melt viscosity as well as their inherent high stiffness and strength, high use temperature, and excellent chemical resistance and low coefficient of expansion. In most of the blends was used LCP of 40 mol % of poly(ethylene terephthalate) (PET) and 60 mol % of p‐acetoxybenzoic acid (PABA). In this work, blends of several copolyesters having various PABA compositions from 10 to 70 mol % and poly(butylene terephthalate) (PBT) were prepared and their rheological and thermal properties were investigated. For convenience, the copolyesters were designated as PETA‐x, where x is the mol % of PABA. It was found that PET‐60 and PET‐70 copolyesters decreased the melt viscosity of PBT in the blends and those PBT/PETA‐60 and PBT/PETA‐70 blends showed different melt viscosity behaviors with the change in shear rate, while blends of PBT and PET‐x having less than 50 mol % of PABA exhibited totally different rheological behaviors. The blends of PBT with PETA‐50, PETA‐60, and PETA‐70 showed the morphology of multiple layers of fibers. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1797–1806, 1999     

Reactive blending as a tool for obtaining poly(ethylene terephthalate)-based engineering materials with tailored properties

The structure and properties of blends of poly(ethylene terephthalate) (PET) with poly(trimethylene terephthalate) (PTT) at PTT concentration ≤30 wt.%, obtained with three different methods: from solution, melt extrusion, and direct spinning, are investigated. Relationships between the method of preparation and properties of blends are established. All blends show glass transition temperature at values determined by composition, and crystallization properties also dependent on the preparation method. Blends obtained from solution show separated melting of components. For blends obtained from the melt only PET crystallizes. The melting temperature decreases with the residence time of the melt at high temperatures, due to occurrence of ester exchange reactions. It is shown that reactive blending of PET/PTT mixtures occurring during preparation is a versatile route for obtainment of engineering materials with good mechanical properties, high crystallinity, glass transition temperature lower than that of PET, and melting temperature that may be controlled by the processing conditions.     

Non-isothermal Crystallization of Poly(ethylene terephthalate) with Poly(oxybenzoate-p-trimethylene terephthalate) Copolymer

The influence of a poly(oxybenzoate-p-trimethylene terephthalate) copolymer, designated T64, on the non-isothermal crystallization process of poly(ethylene terephthalate) (PET) was investigated. All samples were prepared by solution blending in a 60/40 by weight phenol/tetrachloroethane solvent at 50°C. The solidification process strongly depended on cooling rate and composition of system. The crystallization rate of blends was estimated by crystallization rate parameter (CRP) and crystallization rate coefficient (CRC). From these results of CRP and CRC, it was predicted that the overall non-isothermal crystallization rate of PET would be accelerated by blending with 1–15 wt% of T64. The acceleration of PET crystallization rate was most pronounced in the PET/T64 blends with 5 wt% T64. The observed changes in crystallization behavior are explained by the effect of the physical state of the copolyester during PET crystallization as well as the amount of copolymer in the blends. An Ozawa plot was used to analyze the data of non-isothermal crystallization. The obvious curvature in the plot indicated that the Ozawa model could not fit the PET/T64 blend system well, and there was an abrupt change in the slope of the Ozawa plot at a critical cooling rate.