Compatibility studies of blends of polycarbonate and poly(ethylene terephthalate)

Blends of bisphenol-A polyarbonate (PC) and poly(ethylene terephthalate) (PET) has been investigated by differential scanning calorimetry and scanning electron microscopy. Blends were prepared by screw extrusion and solution casting with weight fractions of PC in the blends varying from 0.90 to 0.10. From the measured glass transition temperature (T_g) and apparent weight fractions of PC and PET dissolved in each phase, it appears that PET dissolves more in the PC-rich phase than does the PC in the PET-rich phase. The composition-dependent values of the Flory–Huggins polymer–polymer–interaction parameter were determined and found to be from 0.054 to 0.037 for extruded blends at 275°C and from 0.058 to 0.040 for solution casting at 25°C. The interaction parameter decreases with increasing PET concentration. This result is consistent with the values of the T_gs, the microscopy study, and the measured extrudate swell ratios which show that compatibility increases more in the PET-rich compositions than in the PC-rich compositions. The PC–PET blends are not microscopically miscible for all the blend compositions.     

Can random copolymers serve as effective polymeric compatibilizers?

We investigate the compatibilizing performance of a random copolymer in the melt state, using transmission electron microscopy. Blends of polystyrene (PS) and poly(methyl methacrylate) (PMMA) are chosen as a model system, and a random copolymer of styrene and methyl methacrylate (SMMA) with 70 wt % styrene is used as a compatibilizer. From TEM photographs it is clear that SMMA moves to the interface between PS and PMMA domains during melt mixing, and forms encapsulating layers. However, the characteristic size of the dispersed phase increases gradually with annealing time for all blend systems studied. This demonstrates that the encapsulating layer of SMMA does not provide stability against static coalescence, which calls into question the effectiveness of random copolymers as practical compatibilizers. We interpret the encapsulation by random copolymers in terms of a simple model for ternary polymer blends. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2835–2842, 1997     

Investigations of transesterification in PC/PBT melt blends and the proof of immiscibility of PC and PBT at completely suppressed transesterification

The miscibility of polycarbonate PC and poly(butylene terephthalate) PBT is controversially discussed in the literature. Partial miscibility has been generally found in melt blends of the two polymers. However, in solution cast blends they were found to be immiscible. It is known that the transesterification takes place in the melt. Copolyesters formed by the transesterification change the compatibility of PC and PBT. In this work PC/PBT melt blends of various composition were investigated in dependence on the copolyester content by means of DSC and NMR. It can be shown that the time regime of the thermal treatment in the melt determines the transesterification degree. The PBT crystallization behavior is strongly influenced by both the PC and copolyester content. The glass transition temperatures of the PBT-rich and PC-rich phase approach each other with the increasing copolyester content. The analysis of the glass transition behavior permits the conclusion that PC and PBT are inherently immiscible provided that the copolyester content is exactly zero. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2161–2168, 1997     

The effect of interfacial miscibility on the cell morphology of polyethylene terephthalate/bisphenol a polycarbonate blend foams

Annealing polyethylene terephthalate (PET)/polycarbonate (PC) blends enhance the transesterification reaction and increase the amount of copolymer at the interface of both polymers. The copolymer enhances the compatibility of PET with PC, because it contains both PET and PC blocks, which causes the interface between PET and PC to become fuzzy. When the PET/PC undergoes batch physical foaming with CO₂, the copolymer significantly changes the resulting cell morphology, that is, the annealing time. Before annealing or in the absence of the copolymer, bubble nucleation occurs and dominates growth at the interface. When the PET/PC blends are annealed, the interface impedes bubble nucleation and growth. The polymer is stretched at the interface by bubble growth, forming fibril‐like structures connecting two polymer domains at the interface. Increased annealing time causes the interface to become more homogeneous and makes heterogeneous bubble nucleation difficult. At higher copolymer concentrations, the interface of PET and PC becomes fuzzy and the cell morphology becomes like those of foamed homogeneous polymers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Comparison of statistical and blocky copolymers of ethylene terephthalate and ethylene 4,4′‐bibenzoate based on thermal behavior and oxygen transport properties

Poly(ethylene terephthalate) (PET) was blended with a frustrated liquid‐crystalline polymer, poly(ethylene terephthalate‐co‐4,4′‐bibenzoate) (PETBB55), in the weight ratio 70:30. Under the melt conditions used for blending, NMR analysis showed that some transesterification had occurred. Accordingly, the blended product resembled a blocky copolymer more closely than it did a physical blend. A random copolymer with the same composition was synthesized for comparison. The study examined the effect of the comonomer distribution (blocky vs random) on the thermal behavior and oxygen transport properties of the glassy and cold‐drawn polymers. The glass‐transition temperatures and the crystallization behavior suggested that the PETBB55 blocks phase‐separated as very small domains. Higher levels of orientation, as indicated by higher densities and higher trans glycol fractions, were achieved by the cold drawing of the blocky copolymer. It was speculated that the cold drawing of the blocky copolymer at temperatures up to the glass‐transition temperature of the PETBB55 blocks produced highly oriented PETBB55 domains. Constraints imposed by connections between PET and the PETBB55 blocks prevented the relaxation of the continuous PET phase, even at temperatures well above the glass‐transition temperature of the PET blocks. In this sense, the blocky copolymer embodied the concept of a self‐reinforcing polymer. As a result, an improved oxygen barrier was obtained over a wider range of cold‐draw temperatures with the blocky copolymer. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 289–307, 2003     

A novel method for the pore size control of the battery separator using the phase instability of the ternary mixtures

The battery separator plays a key role in determining the capacity of the battery. Since separator performance mainly depends on the pore size of membrane, development of a technique for the fabrication of the membrane having controlled pore size is essential in producing a highly functional battery separator. In this study, microporous membranes having the desired pore size were produced via thermally‐induced phase separation (TIPS) process. Control of the phase boundaries of polymer‐diluent blends is the main concern in manipulating pore size in TIPS process, because pore size mainly depends on the temperature gap between phase separation temperature of the blend and the crystallization temperature of polymer. Microporous membranes having controlled pore size were produced from polyethylene (PE)/dioctyl phthalate (DOP) blends, PE/isoparaffin blends, and polymer/diluent‐mixture ternary blends, that is, PE/(DOP/isoparaffin) blends. PE/DOP binary blends and PE/(DOP/isoparaffin) ternary blends exhibited typical upper critical solution temperature (UCST) type phase behavior, while PE formed a homogeneous mixture with isoparaffin above the crystallization temperature of PE. When the mixing ratio of polymer and diluent‐mixture was fixed, the phase separation temperature of PE/diluent‐mixture blend first increased with increasing DOP content in the diluent‐mixture, went through a maximum centered at about 80 wt % DOP and then decreased. Furthermore, the phase separation temperatures of the PE/diluent‐mixture blends were always higher than that of the PE/DOP blend when diluent‐mixture contained more than or equal to 20 wt % of DOP. Average pore size of microporous membrane prepared from PE/DOP blend and that prepared from PE/isoparaffin blend were 0.17 and 0.07 μm, respectively. However, average pore size of microporous membrane prepared from ternary blends was varied from 0.07 to 0.5 μm by controlling diluent mixing ratio. To understand the phase behavior of ternary blend, phase instability of the ternary mixture was also explored. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2025–2034, 2006     

Phase separation in semicrystalline blends of poly(phenylene sulfide) and poly(ethylene terephthalate). I. Preparation of poly(phenylene sulfide)-graft-poly(ethylene terephthalate) copolymers by ester interchange and characterization utilizing the model compound 2,4-bis(phenylthio benzoic acid)

Blends of carboxyl functionalized poly(phenylene sulfide) (PPS) and poly(ethylene terephthalate) (PET) were shown to undergo an ester interchange reaction during melt blending. Pendent carboxyl functionality randomly incorporated along the PPS chain reacts with the ester moiety of PET to form a graft copolymer. A model compound, 2,4-bis(phenylthio benzoic acid), has been synthesized to assist in defining the level of carboxyl functionality on the PPS chain. Evidence of the grafting reaction has been gathered from infrared spectroscopy, solubility measurements, and electron microscopy. When added to blends of PPS and PET homopolymers, the graft copolymer significantly reduces the average domain size of the dispersed phase across the entire composition range. This study describes the role that graft copolymers formed by ester interchange reactions can play in compatibilizing this immiscible blend system, with particular focus on the conditions leading to increased grafting efficiency. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3473–3485, 1999     

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.     

A polymer of bisphenol A and bisphenol A diglycidyl ether and its blends with poly(styrene‐co‐acrylonitrile): In situ polymerization preparation,morphology, and mechanical properties

The poly(hydroxy ether of bisphenol A)‐based blends containing poly(acrylontrile‐co‐styrene) (SAN) were prepared through in situ polymerization, i.e., the melt polymerization between the diglycidy ether of bisphenol A (DGEBA) and bisphenol A in the presence of poly(acrylontrile‐co‐styrene) (SAN). The polymerization reaction started from the initial homogeneous ternary mixture of SAN/DGEBA/bisphenol A, and the phenoxy/SAN blends with SAN content up to 20 wt % were obtained. Both the solubility behavior and Fourier transform infrared (FTIR) spectroscopy studies demonstrate that no intercomponent reaction occurred in the reactive blend system. Differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and scanning electronic microscopy (SEM) were employed to characterize the phase structure of the as‐polymerized blends. All the blends display the separate glass transition temperatures (T_g's); i.e., the blends were phase‐separated. The morphological observation showed that all the blends exhibited well‐distributed phase‐separated morphology. For the blends with SAN content less than 15 wt %, very fine SAN spherical particles (1–3 μmm in diameter) were uniformly dispersed in a continuous matrix of phenoxy and the fine morphology was formed through phase separation induced by polymerization. Mechanical tests show that the blends containing 5–15 wt % SAN displayed a substantial improvement of tensile properties and Izod impact strength, which were in marked contrast to those of the materials prepared via conventional methods. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 525–532, 1999     

Effect of dispersed phase composition on morphological and mechanical properties of PET/EVA/PP ternary blends

Immiscible ternary blends of PET/EVA/PP (PET as the matrix and (PP/EVA) composition ratio = 1/1) were prepared by melt mixing. Scanning electron microscope results showed core‐shell type morphology for this ternary blend. Binary blends of PET/PP and PET/EVA were also prepared as control samples. Two grades of EVA with various viscosities, one higher and the other one lower than that of PP, were used to investigate the effect of components' viscosity on the droplet size of disperse phase. The effect of interfacial tension, elasticity, and viscosity on the disperse phase size of both binary and ternary blends was investigated. Variation of tensile modulus of both binary and ternary blends with dispersed phase content was also studied. Experimental results obtained for modulus of PET/EVA binary blends, showed no significant deviations from Takayanagi model, where considerable deviations were observed for PET/PP binary blends. Here, this model that has been originally proposed for binary blends was improved to become applicable for the prediction of the tensile modulus of ternary blends. The new modified model showed good agreement with the experimental data obtained in this study. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 251–259, 2010     

An intimate polycarbonate/poly(methyl methacrylate)/poly(vinyl acetate) ternary blend via coalescence from their common inclusion compound with γ‐cyclodextrin

In this study, we successfully report an intimate ternary blend system of polycarbonate (PC)/poly(methyl methacrylate) (PMMA)/poly(vinyl acetate) (PVAc) obtained by the simultaneous coalescence of the three guest polymers from their common γ‐cyclodextrin (γ‐CD) inclusion compound (IC). The thermal transitions and the homogeneity of the coalesced ternary blend were studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The observation of a single, common glass transition strongly suggests the presence of a homogeneous amorphous phase in the coalesced ternary polymer blend. This was further substantiated by solid‐state ¹³C NMR observation of the T_1ρ(¹H)s for each of the blend components. For comparison, ternary blends of PC/PMMA/PVAc were also prepared by traditional coprecipitation and solution casting methods. TGA data showed a thermal stability for the coalesced ternary blend that was improved over the coprecipitated blend, which was phase‐segregated. The presence of possible interactions between the three polymer components was investigated by infrared spectroscopy (FTIR). The analysis indicates that the ternary blend of these polymers achieved by coalescence from their common γ‐CD–IC results in a homogeneous polymer blend, possibly with improved properties, whereas coprecipitation and solution cast methods produced phase separated polymer blends. It was also found that control of the component polymer molar ratios plays a key role in the miscibility of their coalesced ternary blends. Coalescence of two or more normally immiscible polymers from their common CD–ICs appears to be a general method for obtaining well‐mixed, intimate blends. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4182–4194, 2004     

PET/PEN共混物的相容性与酯交换反应

通过用1H-NMR对聚对苯二甲酸乙二酯(PET)与聚2,6-萘甲酸乙二酯(PEN)、PET/PEN共聚物的共混物酯交换反应的研究,测得了反应速率常数、反应活化能和诱导期.根据酯交换反应程度和不同反应温度下的诱导期探讨了酯交换反应与相容性的关系,认为PET与PEN的相容导致或增强了酯交换反应,即相容性是酯交换的必要条件;同时酯交换的发生又促进了PET与PEN的相容.酯交换和相容是聚酯共混物熔融时相互关联的两个过程.     

Compatibilizing effect of a graft copolymer on bacterial poly(3‐hydroxybutyrate)/poly(methyl methacrylate) blends

Blends of isotactic (natural) poly(3‐hydroxybutyrate) (PHB) and poly(methyl methacrylate) (PMMA) are partially miscible, and PHB in excess of 20 wt % segregates as a partially crystalline pure phase. Copolymers containing atactic PHB chains grafted onto a PMMA backbone are used to compatibilize phase‐separated PHB/PMMA blends. Two poly(methyl methacrylate‐g‐hydroxybutyrate) [P(MMA‐g‐HB)] copolymers with different grafting densities and the same length of the grafted chain have been investigated. The copolymer with higher grafting density, containing 67 mol % hydroxybutyrate units, has a beneficial effect on the mechanical properties of PHB/PMMA blends with 30–50% PHB content, which show a remarkable increase in ductility. The main effect of copolymer addition is the inhibition of PHB crystallization. No compatibilizing effect on PHB/PMMA blends with PHB contents higher than 50% is observed with various amounts of P(MMA‐g‐HB) copolymer. In these blends, the graft copolymer is not able to prevent PHB crystallization, and the ternary PHB/PMMA/P(MMA‐g‐HB) blends remain crystalline and brittle. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1390–1399, 2002     

Phase separation,porous structure,and cure kinetics in aliphatic epoxy resin containing hyperbranched polyester

Thermosetting blends of an aliphatic epoxy resin and a hydroxyl‐functionalized hyperbranched polymer (HBP), aliphatic hyperbranched polyester Boltorn H40, were prepared using 4,4′‐diaminodiphenylmethane (DDM) as the curing agent. The phase behavior and morphology of the DDM‐cured epoxy/HBP blends with HBP content up to 40 wt % were investigated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and scanning electron microscopy (SEM). The cured epoxy/HBP blends are immiscible and exhibit two separate glass transitions, as revealed by DMA. The SEM observation showed that there exist two phases in the cured blends, which is an epoxy‐rich phase and an HBP‐rich phase, which is responsible for the two separate glass transitions. The phase morphology was observed to be dependent on the blend composition. For the blends with HBP content up to 10 wt %, discrete HBP domains are dispersed in the continuous cured epoxy matrix, whereas the cured blend with 40 wt % HBP exhibits a combined morphology of connected globules and bicontinuous phase structure. Porous epoxy thermosets with continuous open structures on the order of 100–300 nm were formed after the HBP‐rich phase was extracted with solvent from the cured blend with 40 wt % HBP. The DSC study showed that the curing rate is not obviously affected in the epoxy/HBP blends with HBP content up to 40 wt %. The activation energy values obtained are not remarkably changed in the blends; the addition of HBP to epoxy resin thus does not change the mechanism of cure reaction of epoxy resin with DDM. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 889–899, 2006     

Control of phase separation behavior of PC/PMMA blends and their application to the gas separation membranes

Gas transport and thermodynamic properties for the blends of polycarbonate (PC) and polymethylmethacrylate (PMMA) were studied. To explore glass transition temperatures of blends and their phase separation temperatures due to a lower critical solution temperature, LCST, a type of phase boundary, transparent blend films that are miscible and do not contain solvent-induced PC crystals were prepared by controlling molecular weights of each component. The average value of interaction energy densities between PC and PMMA obtained from the phase boundaries and the equation of a state theory based on the lattice fluid model was 0.04 cal/cm³. This result confirmed that miscibility of PC and PMMA blends at equilibrium depends upon the molecular weights of components. Gas transport properties of miscible blends and immiscible blends having the same chemical components and composition but a difference in morphology were examined at 35°C and 1 atm for the gases N₂ and O₂. Permeability and apparent diffusion coefficients were ranked in the order of the immiscible blend having a domain–matrix structure > the immiscible blend having an interconnected structure > the miscible blend. These results might be related to the differences in the local chain motions that depend on the intermolecular mixing level. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2950–2959, 1999     

Transreactions in poly trimethylene terephthalate/bisphenol-A polycarbonate (PC) blends analysed by pressure-volume-temperature measurements

The effect of annealing on the miscibility and thermal properties of poly trimethylene terephthalate (PTT)/bisphenol-A polycarbonate (PC) blends was examined using pressure-volume-temperature (PVT) measurements. The PTT/PC blends were thermally annealed at 260 °C for different times to induce various extents of transesterification reactions between the two polymers. The non-annealed blends are immiscible and exhibit the thermal properties of the blend components. Upon annealing, the original semi-crystalline morphology transforms to an increasingly amorphous nature. PVT and WAXS analysis confirmed that the PTT/PC blends completely lost their crystallinity when annealed at 260 °C for a period of 120 min or longer, indicating the formation of random co-polyesters due to chemical transreactions between the PTT and PC. The further increase in the specific volume with annealing time also indicates that after reaching a completely amorphous co-polymer the transesterification continuous until a fully random copolymer is formed.     

四氧化疗染色法在PC／PET共混体研究中的应用

以RuO4为双酚A聚碳酸酯／聚对苯二甲酸乙二酯（PC／PET）共混体系的薰染剂，可成功地用透射电观察其微观形态和相结构，该体系两相微观结构受原料分子量，组成和溶剂的影响。     

聚甲基乙烯基醚的局部构象

采用低能构象方法和构象扫描方法,在Dreiding力场下,对含有3种不同侧基取向的PVME的全同二单元体和间同二单元体进行全松弛优化.通过统计平均得到PVME各种构象状态的几何参数和构象能.由统计平均的结果确立了包含侧基所有可能取向信息的PVME链的RIS模型,并利用MontCarlo方法计算了PVME链的特征比,结合实验数据讨论了侧基取向行为的影响.     

Fourier - transform infrared - spectrometric investigation of blends of terephthalic polyesters with polycarbonate

Blends of polycarbonate (PC) and poly(ethyleneterephthalate) (PET) or poly(butyleneterephthalate) (PBT) heated above the melting temperature of the crystalline component show transesterification reactions. The crystallizability of the resulting system (mixture of copolyesters with homopolymers) decreases with time. Blends of PET and PC loose their crystallizability after 10 - 20 min at 543 K. After that treatment samples with low content of PC have lost the characteristic IR absorptions of PC. Transesterification is faster in blends of PBT and PC: after 3–15 min at 543 K the crystallizability has vanished. After transesterification has reached equilibrium a homogeneous statistical copolymer has developed from the homopolymers.     

Particulate growth in phase-separated polymer blends

Particle coarsening was investigated in polymer blends containing a minor phase volume of 23% produced by compositional quenching. The scaling exponents for three binary blends (polystyrene/polybutadiene, polystyrene/polyisoprene, and polystyrene/S-B random copolymer) were in reasonable agreement with the expected value of 0.33. The scaling exponent for a ternary blend containing an amphiphile (polystyrene/polybutadiene/S-B block copolymer) was substantially lower at 0.14. The particle size distributions for all the blends were broader than the self-similar distribution expected for Ostwald ripening and became increasingly broad with time. These distributions fit a two parameter coalescence model in which the probability of coalescence is proportional to the particle diameter. However, Ostwald ripening appears to make some contribution, particularly at early times. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2191–2196, 1998