Miscibility and transesterification in ternary blends of poly(ethylene naphthalate)/poly(trimethylene terephthalate)/poly(ether imide)

Miscibility and morphology of poly(ethylene 2,6-naphthalate)/poly(trimethylene terephthalate)/poly(ether imide) (PEN/PTT/PEI) blends were investigated by using a differential scanning calorimeter (DSC), optical microscopy (OM), wide-angle X-ray diffraction (WAXD), and proton nuclear magnetic resonance (¹H-NMR). In the ternary blends, OM and DSC results indicated immiscible properties for polyester-rich compositions of PEN/PTT/PEI blends, but all compositions of the ternary blends were phase homogeneous after heat treatment at 300 °C for more than 30 min. An amorphous blend with a single T _g was obtained in the final state, when samples were annealed at 300 °C. Experimental results from ¹H-NMR identified the production of PEN/PTT copolymers by so-called “transesterification”. The influence of transesterification on the behaviors of glass transition and crystallization was discussed in detail. Study results identified that a random copolymer promoted the miscibility of the ternary blends. The critical block lengths for both PEN and PTT hindered the formation of crystals in the ternary blends. Finally, the transesterification product of PEN/PTT blends, ENTT, was blended with PEI. The results for DSC and OM demonstrated the miscibility of the ENTT/PEI blends.     

Miscibility of poly(ethylene terephthalate)/poly(ethylene 2,6-naphthalate) blends by transesterification

The effects of transesterification on the miscibility of poly(ethylene terephthalate)/poly(ethylene 2,6-naphthalate) were studied. Blends were obtained by solution precipitation at room temperature to avoid transesterification during blend preparation. The physical blends and transesterified products were analyzed by wide-angle x-ray scattering, differential scanning calorimetry, and nuclear magnetic resonance spectroscopy. It was found that the physical blends are immiscible and when the extent of transesterification reaches 50% of the completely randomized state, independent of blend composition, the blends are not crystallizable and show a single glass transition temperature between those of starting polymers. The interchange reactions were significantly influenced by annealing temperature and time but negligibly by blend composition. © 1996 John Wiley & Sons, Inc.     

Structure,properties and interfacial interactions in poly(lactic acid)/polyurethane blends prepared by reactive processing

Polyurethane elastomers are promising candidates for the impact modification of PLA producing blends for example for biomedicine. Poly(lactic acid) (PLA)/polyurethane elastomer (PU) blends were prepared by reactive processing and physical blending as comparison. The blends were characterized by a number of techniques including microscopy (scanning electron microscopy, SEM, and atomic force microscopy, AFM), rotational viscometry, thermal (dynamic mechanical analysis, DMA), and mechanical (tensile) measurements. The analysis and comparison of the structure and properties of physical and reactor blends proved the successful coupling of the phases. Coupling resulted in more advantageous structure and superior mechanical properties compared to those of physical blends as confirmed by morphology, macroscopic properties and the quantitative estimation of interfacial interactions. Structural studies and the composition dependence of properties indicated the formation of a submicron, phase-in-phase structure which positively influenced properties at large PU contents. The results strongly support that reactive processing is a convenient, cost-effective and environmentally friendly technique to obtain blends with superior properties.     

Miscibility of biodegradable poly(propylene succinate)/poly(propylene adipate) blends: Effect of the transesterification reactions

The miscibility of poly(propylene succinate)/poly(propylene adipate) blends was investigated by means of DSC, WAXS and NMR techniques. Poly(propylene succinate) and poly(propylene adipate) were found to be completely immiscible in as blended-state. The miscibility changes upon extended mixing at elevated temperature: for enough long mixing time, the original two phases gradually merged into a single one because of transesterification reactions. The NMR analysis showed that the transesterifications led to block copolymers whose average sequence length decreased as the mixing time is increased at a fixed temperature. Upon very long mixing time (150 min), all PPS and PPA chains are fully transformed into a random copolymer characterized by a single amorphous phase.     

Influence of chain extension on the compatibilization and properties of recycled poly(ethylene terephthalate)/linear low density polyethylene blends

Polymeric methylene diphenyl diisocyanate (PMDI) was added as chain extender to a blend of recycled poly(ethylene terephthalate) (R-PET) and linear low density polyethylene (LLDPE) with compatibilizer of maleic anhydride-grafted poly(styrene-ethylene/butadiene-styrene) (SEBS-g-MA). Hydroxyl end groups of PET can react with both isocyanate groups of PMDI and maleic anhydride groups of SEBS-g-MA, which are competing reactions during reactive extrusion. The compatibility and properties of the blends with various contents of PMDI were systemically evaluated and investigated. WAXD results and SEM observations indicated that chain extension inhibits the reaction between PET and SEBS-g-MA. As the PMDI content increased, the morphology of dispersed phase changed from droplet dispersion to rodlike shape and then to an irregular structure. The DSC results showed that the crystallinity of PET decreased in the presence of PMDI, and the glass transition temperature (T_g) of PET increased with addition of 0-0.7 w% PMDI. The impact strength of the blend with 1.1 w% PMDI increased by 120% with respect to the blend without PMDI, accompanied by only an 8% tensile strength decrease. It was demonstrated that the chain extension of PET with PMDI in R-PET/LLDPE/SEBS-g-MA blends not only decreased the compatibilization effect of SEBS-g-MA but also hindered the crystallization of PET.     

Influence of compatibilization on the mechanical behavior of poly(trimethylene terephthalate)/poly(ethylene-octene) blends

Poly(trimethylene terephthalate) (PTT) based blends toughened with up to 30 wt.% of a partially maleinized poly(ethylene-octene) copolymer (mPEO) were obtained by melt mixing. The blends were composed of two pure amorphous phases and a partially crystalline PEO phase. The rubber modification clearly compatibilized the blends leading to a decrease in the dispersed phase size. The decrease was not enough to attain the brittle-tough transition, but an increase in the shear rate gave rise to an additional decrease in the dispersed phase size and in the interparticle distance (IDc) that led to very high toughness values (15-fold the notched impact strength of the matrix) at rubber contents above 25 wt.%. The critical interparticle distance of the blends was 0.17 μm. A comparison between this IDc and those of PBT/mPEO and PET/mPEO blends was explained in terms of their interfacial tensions.     

Studies of miscibility,transesterification and crystallization in blends of poly(ethylene terephthalate) and Poly(ethylene-2,6-naphthalene dicarboxylate)

Blends of poly(ethylene terephthalate) (PET) and poly(ethylene-2,6-naphthalene dicarboxylate) (PEN) were obtained by coprecipitation from solution followed by melt-pressing for different timest _mand quenching in iced water. When the melt-pressing time was 0.2 and 0.5 min, two glass transition temperaturesT _gwere observed by means of dynamic mechanical analysis (DMA), indicating that there are two phases present, a PEN-rich phase and a PET-rich phase. The differential scanning calorimetry (DSC) curves show two crystallization peaks and two melting peaks which, according to wide-angle x-ray scattering (WAXS) measurements, can be attributed to PET and PEN, respectively. In the case oft _m=2 min or longer, a single value ofT _gand thus a single phase is found to exist. Fort _m=10 min and 45 min no crystallization and melting at all is observed during heating with 10°C/min, indicating that a copolyester of PET and PEN has been formed by transesterfication during melt-pressing.Time-resolved WAXS measurements during isothermal crystallization show that, in the blend, the half-time of crystallization of PET is different from that of PEN, and not the same as that which is found in the pure polymer.Dedicated with best wishes to Prof. Dr. E.W. Fischer on the occasion of his 65th birthday     

Transesterification kinetics in the reactive blends of liquid crystalline copolyesters and poly(ethylene terephthalate)

The transesterification kinetics of poly(ethylene terephthalate) (PET)/copoly(oxybenzoate-p-terephthalate) (liquid crystalline polymer, LCP) (70/30 by weight) in the presence of small amount of bis(2-oxazoline) (BOZ) as chain extender was studied by using 1H nuclear magnetic resonance. The kinetic data was treated as a second-order reversible reaction, and it was found that the rate constants of transesterification at 270, 280 and 290 °C were 1.55×10⁻², 2.20×10⁻² and 3.01×10⁻² min⁻¹, respectively, the value of which was higher than the blend without addition of BOZ, 1.26×10⁻² min⁻¹, and the activation energy of PET/LCP transesterification was 84.4 kJ mol⁻¹.     

Influence of cobalt complex on thermal properties of poly(ethylene terephthalate)/polycarbonate blend

The effects of processing time and concentration of cobalt acetylacetonate III complex in poly(ethylene terephthalate)/polycarbonate reactive blending were investigated. The blend was prepared in an internal mixer at 270°C, 60 rpm, at different processing times (5–20 min) and catalyst concentration (0.00625–0.075 mass%). The reaction product was evaluated by differential scanning calorimetry (DSC), thermogravimetry (TG) and wide angle X-rays scattering (WAXS). In general, the DSC curves showed two glass transition temperatures (T _g’s) close to each homopolymer, independent of the processing time and complex’s concentration, suggesting the presence of two phases: one rich in PET and other one rich in PC. In all cases, melting temperature (T _m), cold crystallization temperature (T _cc) and crystallinity degree (X _c) were progressively reduced with blending conditions. The TG curves presented two decays. The first one represented the PET rich phase and the other one was related to the PC phase. The WAXS diffractograms showed that the Bragg’s angle and interplanar spacing of PET remaining practically unchanged.     

Effect of transesterification products on the miscibility and phase behavior of poly(trimethylene terephthalate)/bisphenol A polycarbonate blends

Blends of poly(trimethylene terephthalate)/bisphenol A polycarbonate (PTT/PC) with different compositions were prepared by melt blending. The effect of transesterification on the miscibility and phase behavior of the blends was studied using DSC, DMA, and ¹H NMR. The DMA results revealed a two-phase system with partial miscibility. DSC thermograms of the first heating scan showed a crystallizable system in which addition of PC-phase reduces the degree of crystallinity. However, the cooling and also the second heating scans revealed the complete miscibility of all the blends. It was concluded that annealing at 300 °C (to remove thermal history of the blends) caused the constituents to undergo the transesterification reaction, which changes the blend to a miscible system. The miscibility is due to formation of block copolymers with different block lengths which also suppress the crystallization of the system. The degree of randomness and sequence lengths of the copolymers were determined to analyze the extent of transesterification reaction and structure of the system. It was observed that as the reaction progresses, the degree of randomness increases and the sequence length of the copolymers decreases. Moreover, both increase of reaction time and temperature increased the extent of reaction. The results of DSC and ¹H NMR showed that a small amount of reaction is needed to change this system to a miscible blend.     

Miscibility and compatibilization of poly(trimethylene terephthalate)/acrylonitrile-butadiene-styrene blends

Poly(trimethylene terephthalate)/acrylonitrile-butadiene-styrene (PTT/ABS) blends were prepared by melt processing with and without epoxy or styrene-butadiene-maleic anhydride copolymer (SBM) as a reactive compatibilizer. The miscibility and compatibilization of the PTT/ABS blends were investigated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), capillary rheometer and scanning electron microscopy (SEM). The existence of two separate composition-dependent glass transition temperatures (T_gs) indicates that PTT is partially miscible with ABS over the entire composition range. In the presence of the compatibilizer, both the cold crystallization and glass transition temperatures of the PTT phase shifted to higher temperatures, indicating their compatibilization effects on the blends.The PTT/ABS blends exhibited typical pseudoplastic flow behavior. The rheological behavior of the epoxy compatibilized PTT/ABS blends showed an epoxy content-dependence. In contrast, when the SBM content was increased from 1 wt% to 5 wt%, the shear viscosities of the PTT/ABS blends increased and exhibited much clearer shear thinning behavior at higher shear rates. The SEM micrographs of the epoxy or SBM compatibilized PTT/ABS blends showed a finer morphology and better adhesion between the phases.     

Compatible and tearing properties of poly(lactic acid)/poly(ethylene glutaric‐co‐terephthalate) copolyester blends

Fourier transform infrared and nuclear magnetic resonance results suggest that the carboxylic acid groups of poly(lactic acid) (PLA) molecules react with the hydroxyl groups of FePol (FP) molecules during the melt‐blending of PLA_xFP_y specimens. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) experiments of PLA and PLA/FP specimens suggest that only small amounts of poor PLA and/or FP crystals are present in their corresponding melt crystallized specimens. In fact, the percentage crystallinity, peak melting temperature, and onset re‐crystallization temperature values of PLA/FP specimens reduce gradually as their FP contents increase. However, the glass transition temperatures of PLA molecules found by DSC and DMA reduce to a minimum value as the FP contents of PLA_xFP_y specimens reach 6 wt %. Further DMA and morphological analysis of PLA/FP specimens reveal that FP molecules are compatible with PLA molecules at FP contents equal to or less than 6 wt %, as no distinguished phase‐separated FP droplets and tan δ transitions were found on fracture surfaces and tan δ curves of PLA/FP specimens, respectively. In contrast to PLA, the FP specimen exhibits highly deformable and tearing properties. After blending proper amounts of FP in PLA, the inherent brittle deformation and poor tearing behavior of PLA were successfully improved. Possible reasons accounting for these interesting crystallization, compatible and tearing properties of PLA/FP specimens are proposed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 913–920, 2010     

Morphology development and crystallization behavior of poly(ethylene terephthalate)/poly(trimethylene terephthalate) blends

The spherulite morphology and crystallization behavior of poly(ethylene terephthalate) (PET)/poly(trimethylene terephthalate) (PTT) blends were investigated with optical microscopy (OM), small-angle light scattering (SALS), and small-angle X-ray scattering (SAXS). The thermal analysis showed that PET and PTT were miscible in the melt over the entire composition range. The rejected distance of non-crystallizable species, which was represented in terms of the parameter δ, played an important role in determining the morphological patterns of the blends at a specific crystallization temperature regime. The parameter δ could be controlled by variation of the composition, the crystallization temperature, and the level of transesterification. In the case of two-step crystallization, the crystallization of PTT commenced in the interspherulitic region between the grown PET crystals and proceeded until the interspherulitic space was filled with PTT crystals. The spherulitic surface of the PET crystals acted as nucleation sites where PTT preferentially crystallized, leading to the formation of non-spherulitic crystalline texture. The SALS results suggested that the growth pattern of the PET crystals was significantly changed by the presence of the PTT molecules. The lamellar morphology parameters were evaluated by a one-dimensional correlation function analysis. The blends that crystallized above the melting point of PTT showed a larger amorphous layer thickness than the pure PET, indicating that the non-crystallizable PTT component might be incorporated into the interlamellar region of the PET crystals. With an increased level of transesterification, the exclusion of non-crystallizable species from the lamellar stacks was favorable due to the lower crystal growth rates. As a result, the amorphous layer thickness of the PET crystals decreased as the annealing time in the melt state was increased.     

Mechano-optical behavior in poly (ethylene terephthalate)/poly (ether imide) blends

Mechano-optical behavior and related structural evolution during uniaxial stretching of melt miscible poly (ethylene terephthalate) (PET)/poly (ether imide) (PEI) blends were studied near their glass transition temperature using an instrumented machine that measures true stress, true strain and spectral birefringence simultaneously. Stretching from amorphous state, two distinct stress-optical regimes were observed at temperatures between T_g and T_cc (cold crystallization). Near T_g, a typical photoelastic behavior persists until a critical temperature above which temperature independent initial stress optical behavior is observed. At those temperatures above T_g, where glassy behavior is observed, decreasing stretching rate was also found to eliminate this glassy photo elastic regime leading to the observation of a linear initial stress optical behavior that becomes temperature independent as expected from linear stress optical rule. Increasing PEI concentration in the blends suppresses crystallizability and increases temperature at which initial elastic region disappears giving way to pure liquid behavior where linear stress optical behavior is observed. This is attributed to the increase and broadening of the glass transition temperature with the addition of noncrystallizable PEI. In PET/PEI blends, the stress-optical coefficient (SOC), determined in a linear stress optical regime, was found to increase linearly with the increase in PEI concentration.     

Thermal and crystallization characteristics of poly(trimethylene terephthalate)/poly(ethylene naphthalate) blends

Poly(trimethylene terephthalate) (PTT)/poly(ethylene naphthalate) (PEN) blends were miscible in the amorphous state in all of the blend compositions studied, as evidenced by a single, composition-dependent glass transition temperature (T_g) observed for each blend composition. The variation in the T_g value with the blend composition was well predicted by the Gordon-Taylor equation, with the fitting parameter being 0.57. The cold-crystallization peak temperature decreased with increasing PTT content, while the melt-crystallization peak temperature decreased with increasing amount of the minor component. The subsequent melting behavior after both cold- and melt-crystallization exhibited melting point depression, in which the observed melting temperatures decreased with increasing amount of the minor component. During melt-crystallization, both components in the blends crystallized concurrently just to form their own crystals. The blend with 60% w/w of PTT exhibited the lowest total apparent degree of crystallinity.     

Morphology and interpenetrated growth of spherulites in miscible poly(ethylene succinate)/poly(ethylene oxide) blends

Morphology development and growth process of spherulites in miscible poly(ethylene succinate)/poly(ethylene oxide) blends are studied by means of polarizing optical microscopy and atom force microscopy in this paper. Thin films with different film thicknesses were used to follow the growth processes of spherulites and dendrites. It is shown that, when one component spherulite grows, the other component in the melt is always excluded from the spherulite. The excluded component may reenter into the spherulite through diffusion depending on amorphous volume fraction of spherulite and segmental mobility of molecules, which leads to the occurrence of interpenetrated growth. This mechanism was analyzed in detail in this paper.     

Influence of transesterification reactions on the miscibility and thermal properties of poly(butylene/diethylene succinate) copolymers

Poly(butylene/diethylene succinate) block copolymers (PBSPDGS), prepared by reactive blending of the parent homopolymers (PBS and PDGS) in the presence of Ti(OBu)₄, were analyzed by ¹H-NMR, TGA and DSC, in order to investigate the effects of the transesterification reactions on the molecular structure and thermal properties. ¹H-NMR analysis evidenced the formation of copolymers whose degree of randomness increases with the mixing time. The thermal analysis of the melt-quenched samples showed that the melting peak, due to the crystalline phase of PBS, tends to disappear with increasing mixing time and therefore with decreasing the block length in the copolymers. As concern miscibility, a single homogeneous amorphous phase always occurred, independently on block length. Nevertheless, a phase separation, due to the tendency of the PBS blocks to crystallize, was evidenced in the copolymers with long butylene succinate sequences. The results obtained indicated that the block size had a fundamental role in determining the crystallizability and, therefore, phase behavior of the block copolymers.     

The effect of free radical reactions on structure and properties of poly(lactic acid) (PLA) based blends

The blending of PLA with poly(butylene-adipate-co-terephthalate) (PBAT) is a promising strategy to achieve a toughened multiphase material. The blends ductility could be further improved through reactive compatibilization, i.e. inducing the formation of comb PLA-PBAT copolymers during the melt blending. In the present work a non-selective strategy was adopted which consisted in the use of a peroxide, 2,5-Dimethyl-2,5-di(tert-butylperoxy)hexane. The phase morphology development and the final properties (torque, fluidity in the melt, tensile behaviour, thermal and dynamical-mechanical features) of the blends were studied as a function of the peroxide concentration. The elongation at break was improved up to a maximum value thanks to this approach and a corresponding minimum was observed in the value of the dispersed phase diameter. A structural characterization of the macromolecules formed during the reactive process was attempted by using size exclusion chromatography of the blends and comparison with the pure polymers obtained by processing in the presence of the peroxide.     

Non-isothermal crystallization kinetics of poly(trimethylene terephthalate)/poly(ethylene 2,6-naphthalate) blends

The glass-transition temperature and non-isothermal crystallization of poly(trimethylene terephthalate)/poly(ethylene 2,6-naphthalate) (PTT/PEN) blends were investigated by using differential scanning calorimeter (DSC). The results suggested that the binary blends showed different crystallization and melting behaviors due to their different component of PTT and PEN. All of the samples exhibited a single glass-transition temperature, indicating that the component PTT and PEN were miscible in amorphous phase. The value of T_g predicted well by Gordon-Taylor equation decreased gradually with increasing of PTT content. The commonly used Avrami equation modified by Jeziorny, Ozawa theory and the method developed by Mo were used, respectively, to fit the primary stage of non-isothermal crystallization. The kinetic parameters suggested that the PTT content improved the crystallization of PEN in the binary blend. The crystallization growth dimension, crystallization rate and the degree of crystallinity of the blends were increased with the increasing content of PTT. The effective activation energy calculated by the advanced iso-conversional method developed by Vyazovkin also concluded that the value of E_a depended not only on the system but also on temperature, that is, the binary blend with more PTT component had higher crystallization ability and the crystallization ability is increased with increasing temperature. The kinetic parameters U^* and K_g were also determined, respectively, by the Hoffman-Lauritzen theory.