Reactive compatibilization of poly(butylene terephthalate)/low‐density polyethylene and poly(butylene terephthalate)/ethylene propylene diene rubber blends with a bismaleimide

The reactive compatibilization effect of a small molecule, bismaleimide (BMI), on poly(butylene terephthalate) (PBT)/low‐density polyethylene (LDPE) and PBT/ethylene propylene diene (EPDM) rubber blends were investigated. All the blends were prepared by melt blending in the mixing chamber of a Haake Rheocord. The particle size of dispersed phase was reduced by >ten times by adding 1.2 wt % of BMI as observed with scanning electron microscopy. The torque‐time curve recorded during mixing showed that the addition of BMI leads to a significant increase in the viscosity of PBT, LDPE, EPDM, and the blends. This indicates that a chemical reaction has taken place. It was confirmed that free radicals are involved in the reactions because the addition of a stabilizer to the blends has removed all the compatibilizing effect, and the torque‐time curve does not show any increase in viscosity. A possible mechanism of compatibilization is proposed. The shear forces during melt mixing cause the rupture of chemical bond in the polymers, which form macroradicals of PBT, LDPE, or EPDM. These macroradicals react with BMI to form PBT‐BMI‐LDPE or PBT‐BMI‐EPDM copolymers. These in situ‐formed copolymers act as compatibilizers to give a significant refinement of the blend morphology. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2049–2057, 1999     

Reactive compatibilization of polypropylene/polyethylene terephthalate blends

The reactive compatibilization of polypropylene/polyethylene terephthalate (PP/PET) blends by addition of glycidyl methacrylate grafted PP (PP-g-GMA) was studied. Two PP-g-GMA copolymers, containing either 0.2 or 1.2 wt% of GMA, were used as interface modifiers. These were incorporated into PP blends (with either 70 or 90 wt% PET), replacing 1/5 of PP in the system. The use of these modifiers changed the blends' tensile mechanical behavior from fragile to ductile. Blend tensile strength was improved by 10% and elongation at break showed 10 to 20-fold increases while stiffness remained constant. Scanning electron micrographs showed the PP average domain size in injection molded specimens to decrease to the micron/sub-micron size upon addition of the GMA modified resins, while the unmodified blends exhibited heterogeneous morphology comprising large lamellae 10–20 μm wide. The low-GMA graft content PP seemed slightly more efficient than the high GMA content PP in emulsifiying PP/PET blends. The GMA grafting level on PP had very limited effects on the blends' mechanical behavior in the range of GMA graft density provided by the two modified resins investigated.     

Thermal properties and morphology of recycled poly(ethylene terephthalate)/maleic anhydride grafted linear low‐density polyethylene blends

Properties of recycled Poly(ethylene terephthalate) were greatly improved. Recycled PET was blended with LLDPE‐g‐MA by low‐temperature solid‐state extrusion. Mechanical properties of the blends were affected obviously by the added LLDPE‐g‐MA. Elongation at break reaches 352.8% when the blend contains 10 wt % LLDPE‐g‐MA. Crystallization behavior of PET phase was affected by LLDPE‐g‐MA content. Crystallinity of PET decreased with the increase of LLDPE‐g‐MA content. FTIR testified that maleic anhydride group in LLDPE‐g‐MA reacted with the end hydroxyl groups of PET and PET‐co‐LLDPE‐g‐MA copolymers were in situ synthesized. SEM micrographs display that LLDPE‐g‐MA phase and PET phase are incompatible and the compatibility of the blends can be improved by the forming of PET‐co‐LLDPE‐g‐MA copolymer. LLDPE‐g‐MA content was less, the LLDPE‐g‐MA phase dispersed in PET matrix fine. With the increase of LLDPE‐g‐MA content, the morphology of dispersed LLDPE‐g‐MA phase changed from spherule to cigar bar, then to irregular spherule. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Morphological origin of super toughness in poly(ethylene terephthalate)/polyethylene blends

A compatibilization strategy for poly(ethylene terephthalate) (PET) and polyethylene (PE) blends to achieve high toughness is described. Maleic anhydride functionalized styrene–ethylene–butylene–styrene (MA-g-SEBS) block copolymer at 20 pph was found to produce an intricate multidomain morphology in which the two major components (50% PE, 50% PET) and the compatibilizer coexist on a hierarchal order. A portion of the PET was dispersed as interconnected rodlike domains oriented along the injection direction. The rest of the PET and the PE constituted beadlike nano domains which served as the matrix. The blend at all these morphological levels responded to deformation in a cooperative fashion giving rise to a super tough material. That is, a blend whose elongation at break (600%) was superior to its two major components (90% for PET and 300% for PE). © 1993 John Wiley & Sons, Inc.     

Improving poly(ethylene terephthalate)/high-density polyethylene blends by using graft copolymers

The synthesis and the application of graft copolymers prepared from ozonized polyethylene (HDPE) are described. The homopolymer was treated with ozone and then copolymerized with monomers, such as methyl methacrylate, hydroxy ethyl methacrylate, glycidyl methacrylate, maleic anhydride, and ethyl acrylate. The products were used as compatibilizers in HDPE/PET [poly(ethylene terephthate)] blends. The mechanical properties and the influence of graft comonomers are described. The copolymers were characterized by the grafting rate and FTIR spectroscopy.     

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     

Physical properties of poly(ethylene adipate)/low-density polyethylene blends

Mechanical and rheological properties of poly(ethylene adipate) (PEA)/low-density polyethylene (LDPE) blends were investigated. DSC results showed that there is no miscibility between PEA and LDPE. Tensile strength decreases with increasing PEA content, while the modulus increases. Elongation at break decreases with increasing PEA content. A rheological constitutive equation was used for describing and predicting the steady-state shear viscosity of PEA/LDPE blend. The suggested equation was successfully able to describe and predict viscosity of the blend as functions of shear rate and temperature. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1745–1750, 1997     

Reactive compatibilization of the poly(ethylene terephthalate)/liquid crystalline polymer blends by solid epoxy resin as a coupling agent

A selected reactive coupling agent can be served as an effective compatibilizer for certain immiscible and incompatible blends should both blend constituents possess the necessary functional groups that can react with the coupling agent at comparable rates. Solid epoxy resin with two epoxide endgroups per molecule was demonstrated to be an efficient reactive compatibilizer for the incompatible blends of poly(ethylene terephthalate) (PET) and copolyester liquid crystalline polymer (LCP) by functioning as a coupling agent. The main chain structure of the epoxy resin is neither identical not miscible with PET and LCP and tends to reside at interface during melt mixing. This preferential residence gives the epoxy compatibilizer greater opportunity to react with both PET and LCP simultaneously to produce the in situ–formed epoxy-b-LCP mixed copolymer. This in situ–formed mixed copolymer is highly effective in compatibilizing the PET/LCP blends. This reactive epoxy compatibilizer enhances the LCP fibril formation and results in substantial improvements on stiffness and toughness of the PET/LCP blends. © 1996 John Wiley & Sons, Inc.     

Properties of poly(ethylene terephthalate)/poly(ethylene naphthalate) blends

Blends composed of poly(ethylene terephthalate) (PET) as the majority component and poly(ethylene naphthalate)(PEN) as the minority component were melt-mixed in a single screw extruder at various PET/PEN compound ratios. Tensile and flexural test results reveal a good PET/PEN composition dependence, indicating that the compatibility of the blends is effective in a macrodomain. In thermal tests, single transitions for T_g, T_m and T_c (crystallization temperature), respectively, are observed from DSC as well as single T_g from DMA except for 50/50 blends. These results suggests that the compatibility is sufficient down to the submicron level. Moreover, isothermal DSC tests along with Avrami analysis indicate that PET's crystallization is significantly retarded when blended with PEN. Results in this study demonstrate that PEN is a highly promising additive to improve PET's spinnability at high speeds.     

增容PP/回收PET共混物的力学性能

采用熔融挤出法制备了聚丙烯(PP)/增容剂/回收聚对苯二甲酸乙二酯(r-PET)共混物,研究了r-PET、不同增容剂和混合增容剂对PP/r-PET共混物力学性能的影响.r-PET提高了PP的拉伸强度、弯曲强度及其模量,但降低了冲击强度;采用马来酸酐接枝聚丙烯(PP-g-MAH)增容,可提高PP/r-PET共混物的拉伸强度、弯曲强度及其模量,但使冲击强度稍有降低;马来酸酐接枝乙烯-辛烯共聚物(POE-g-MAH)增容或PP-g-MAH/POE-g-MAH混合增容可提高PP/r-PET共混物的冲击强度,且对共混物的拉伸和弯曲强度影响不大.     

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.     

Phase structure and properties of poly(ethylene terephthalate)/high‐density polyethylene based on recycled materials

Blends based on recycled high density polyethylene (R‐HDPE) and recycled poly(ethylene terephthalate) (R‐PET) were made through reactive extrusion. The effects of maleated polyethylene (PE‐g‐MA), triblock copolymer of styrene and ethylene/butylene (SEBS), and 4,4′‐methylenedi(phenyl isocyanate) (MDI) on blend properties were studied. The 2% PE‐g‐MA improved the compatibility of R‐HDPE and R‐PET in all blends toughened by SEBS. For the R‐HDPE/R‐PET (70/30 w/w) blend toughened by SEBS, the dispersed PET domain size was significantly reduced with use of 2% PE‐g‐MA, and the impact strength of the resultant blend doubled. For blends with R‐PET matrix, all strengths were improved by adding MDI through extending the PET molecular chains. The crystalline behaviors of R‐HDPE and R‐PET in one‐phase rich systems influenced each other. The addition of PE‐g‐MA and SEBS consistently reduced the crystalline level (χ_c) of either the R‐PET or the R‐HDPE phase and lowered the crystallization peak temperature (T_c) of R‐PET. Further addition of MDI did not influence R‐HDPE crystallization behavior but lowered the χ_c of R‐PET in R‐PET rich blends. The thermal stability of R‐HDPE/R‐PET 70/30 and 50/50 (w/w) blends were improved by chain‐extension when 0.5% MDI was added. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Miscibility and melting behavior of poly(ethylene terephthalate)/poly(trimethylene terephthalate) blends

The miscibility and melting behavior of binary crystalline blends of poly(ethylene terephthalate) (PET)/poly(trimethylene terephthalate) (PTT) have been investigated with differential scanning calorimetry and scanning electron microscope. The blends exhibit a single composition‐dependent glass transition temperature (T_g) and the measured T_g fit well with the predicted T_g value by the Fox equation and Gordon‐Taylor equation. In addition to that, a single composition‐dependent cold crystallization temperature (T_cc) value can be observed and it decreases nearly linearly with the low T_g component, PTT, which can also be taken as a valid supportive evidence for miscibility. The SEM graphs showed complete homogeneity in the fractured surfaces of the quenched PET/PTT blends, which provided morphology evidence of a total miscibility of PET/PTT blend in amorphous state at all compositions. The polymer–polymer interaction parameter, χ₁₂, calculated from equilibrium melting temperature depression of the PET component was ?0.1634, revealing miscibility of PET/PTT blends in the melting state. The melting crystallization temperature (T_mc) of the blends decreased with an increase of the minor component and the 50/50 sample showed the lowest T_mc value, which is also related to its miscible nature in the melting state. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Reactive processing compatibilization of direct injection molded polyamide‐6/poly(ethylene terephthalate) blends

Finely dispersed blends of polyamide 6 (PA‐6) and poly(ethylene terephthalate) (PET) were obtained by direct injection molding throughout the full composition range. The blends comprised a probably pure PA‐6 phase, and a PET phase that was apparently pure in PET‐rich blends and contained slight reacted PA‐6 amounts in PA‐6‐rich blends. This very complex morphology was characterized by the presence of dispersed particles at three levels and by a very large interface area/dispersed phase volume ratio. The linear ductility behavior was attributed to both the presence of reacted copolymers and the large interface area/dispersed volume ratio, and the synergism in both the Young's modulus and yield stress to the increased orientation of the blends related to that of the pure components. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 564–574, 2005     

Miscibility of poly(ether imide)/poly(ethylene terephthalate) blends

Summary Miscibility of blends of poly(ether imide) (PEI) and poly(ethylene terephthalate) (PET) were studied by differential scanning calorimetry (DSC). Single and composition-dependent T_g's are observed over the entire composition range, indicating that the blends are miscible in the amorphous region. The overall crystallization rate of PET in the blends decreased with increasing the PEI content. The interaction energy density B, which was calculated from the melting point depression of the blends using Nishi-Wang equation, was-5.5 cal/cm³.     

Effect of compatibilization on the oxygen‐barrier properties of poly(ethylene terephthalate)/poly(m‐xylylene adipamide) blends

The improvement of the oxygen‐barrier properties of poly(ethylene terephthalate) (PET) via blending with an aromatic polyamide [poly(m‐xylylene adipamide) (MXD6)] was studied. The compatibilization of the blends was attempted through the incorporation of small amounts of sodium 5‐sulfoisophthalate (SIPE) into the PET matrix. The possibility of a transamidation reaction between PET and MXD6 was eliminated by ¹³C‐NMR analysis of melt blends with 20 wt % MXD6. An examination of the blend morphology by atomic force microscopy revealed that SIPE effectively compatibilized the blends by reducing the MXD6 particle size. Thermal analysis showed that MXD6 had a nucleating effect on the crystallization of PET, whereas the crystallization of MXD6 was inhibited, especially in compatibilized blends. Blending 10 wt % MXD6 with PET had only a small effect on the oxygen permeability of the unoriented blend when it was measured at 43% relative humidity, as predicted by the Maxwell model. However, biaxially oriented films with 10 wt % MXD6 had significantly reduced oxygen permeability in comparison with PET. The permeability at 43% relative humidity was reduced by a factor of 3 in compatibilized blends. Biaxial orientation transformed spherical MXD6 domains into platelets oriented in the plane of the film. An enhanced barrier arose from the increased tortuosity of the diffusion pathway due to the high aspect ratio of MXD6 platelets. The aspect ratio was calculated from the macroscopic draw ratio and confirmed by atomic force microscopy. The reduction in permeability was satisfactorily described by the Nielsen model. The decrease in the oxygen permeability of biaxially oriented films was also achieved in bottle walls blown from blends of PET with MXD6. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1361–1370, 2005     

Miscibility and crystallization kinetics of poly(trimethylene terephthalate)/amorphous poly(ethylene terephthalate) blends

The miscibility and crystallization kinetics of the blends of poly(trimethylene terephthalate) (PTT) and amorphous poly(ethylene terephthalate) (aPET) have been investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). It was found that PTT/aPET blends were miscible in the melt. Thus, the single glass transition temperature (T_g) of the blends within the whole composition range and the retardation of crystallization kinetics of PTT in blends suggested that PTT and aPET were totally miscible. The nucleation density of PTT spherulites, the spherulitic growth, and overall crystallization rates were depressed upon blending with aPET. The depression in nucleation density of PTT spherulites could be attributed to the equilibrium melting point depression, while the depression in the spherulitic growth and overall crystallization rates could be mainly attributed to the reduction of PTT chain mobility and dilution of PTT upon mixing with aPET. The underlying nucleation mechanism and growth geometry of PTT crystals were not affected by blending, from the results of Avrami analysis. POLYM. ENG. SCI., 47:2005–2011, 2007. © 2007 Society of Plastics Engineers     

Recycled poly(ethylene terephthalate)/linear low‐density polyethylene blends through physical processing

Poly(styrene‐ethylene/butylene‐styrene) (SEBS) was used as a compatibilizer to improve the thermal and mechanical properties of recycled poly(ethylene terephthalate)/linear low‐density polyethylene (R‐PET/LLDPE) blends. The blends compatibilized with 0–20 wt % SEBS were prepared by low‐temperature solid‐state extrusion. The effect of SEBS content was investigated using scanning electron microscope, differential scanning calorimeter, dynamic mechanical analysis (DMA), and mechanical property testing. Morphology observation showed that the addition of 10 wt % SEBS led to the deformation of dispersed phase from spherical to fibrous structure, and microfibrils were formed at the interface between two phases in the compatibilized blends. Both differential scanning calorimeter and DMA results revealed that the blend with 20 wt % SEBS showed better compatibility between PET and LLDPE than other blends studied. The addition of 20 wt % of SEBS obviously improved the crystallizibility of PET as well as the modulus of the blends. DMA analysis also showed that the interaction between SEBS and two other components enhanced at high temperature above 130°C. The impact strength of the blend with 20 wt % SEBS increased of 93.2% with respect to the blend without SEBS, accompanied by only a 28.7% tensile strength decrease. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Miscibility and melting in poly(ethylene terephthalate)/ poly(bisphenol-A-carbonate) blends

Summary In the absence of significant tranesterification, blends of poly(ethylene terephthalate) and poly(bisphenol-A carbonate) were found to be almost completely immiscible over the range of compositions studied. Although the observed behavior was sometimes erratic, poly(bisphenol-A carbonate) appears to exert a significant influence on PET melting behavior and normalized heat of fusion.     

Uniaxial orientation and tensile properties of poly(ethylene terephthalate)/poly(ethylene-2,6-naphthalate) blends

Amorphous films of poly(ethylene terephthalate)/poly(ethylene-2,6-naphthalate) (PET/PEN) blends with different blend ratios were uniaxially drawn by solid-state coextrusion and the structure development during solid state deformation was studied. As-prepared blends showed two T_gs. The lower T_g was ∼72 °C, independent of the blend ratio. In contrast, the higher T_g increased with increasing PEN content. Thus, the coextrusion was carried out around the higher T_g of the sample. At a given draw ratio of 5, which was close to the achievable maximum draw ratio, the tensile strength of the drawn samples from the initially amorphous state increased gradually with increasing PEN content. On the other hand, the tensile modulus was found to decrease initially, reaching a minimum at 40-60 wt% PEN, and then increased as the PEN content increased. The results indicate that we can get the drawn films with a moderate tensile modulus and a high tensile strength. The drawn samples from the blends containing 40-60 wt% of PEN showed a maximum elongation at break, and a maximum thermal shrinkage around 100 °C. Also, the degree of stress-induced crystallinity showed a broad minimum around the blend ratio of 50% of PEN. These morphological characteristics explained well the effects of blend ratio on the tensile modulus and strength of drawn PET/PEN blend films.