Effect of composition and molecular structure on the LC phase of PHB-PEN-PET ternary blend

Poly(p-hydroxybenzoic acid) (PHB)–poly(ethylene terephthalate) (PET) 8/2 thermotropic liquid crystalline copolyester, poly(ethylene 2,6-naphthalate) (PEN), and PET were mechanically blended to pursue the liquid crystalline (LC) phase of ternary blends. The torque values of blends with increasing PHB content abruptly decreased above 40 wt % of PHB content because the melt viscosity of ternary blends dropped. Glass transition temperature and melting temperature of blends increased with increasing PHB content. The tensile strength and initial modulus of blends were low at 10 and 20 wt % PHB. However, the blends containing above 30 wt % PHB were improved with increasing PHB content due to the formation of fibrous structure. The blend of 20 wt % PHB formed irregularly dispersed spherical domains, and the blends of 30–40 wt % PHB showed LCP ellipsoidal domains and fibrils. In the polarized optical photographs, the blends of 40 wt % PHB showed pseudo LC phases. The degree of transesterification and randomness of blends were increased with blending time. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 1065–1073, 1998     

Synthesis and properties of reactively compatibilized polyester and polyamide blends

The functionalization of poly(butylene terephthalate) (PBT) has been accomplished in a twin screw extruder by grafting maleic anhydride (MA) using a free radical polymerization technique. The resulting PBT‐g‐MA was successfully used as a compatibilizer for the binary blends of polyester (PBT) and polyamide (PA66). Enhanced mechanical properties were achieved for the blend containing a small amount (as low as 2.5 %) of PBT‐g‐MA compared to the binary blend of unmodified PBT with PA66. Loss and storage moduli for blends containing compatibilizer were higher than those of uncompatibilized blends or their respective polymers. The grafting and compatibilization reactions were confirmed using FTIR and ¹³C NMR spectroscopy. The properties of these blends were studied in detail by varying the amount of compatibilizer, and the improved mechanical behaviour was correlated with the morphology with the help of scanning electron microscopy. Morphology studies also revealed the interfacial interaction in the blend containing grafted PBT. The improvement in the properties of these blends can be attributed to the effective interaction of grafted maleic anhydride groups with the amino group in PA66. The results indicate that PBT‐g‐MA acts as an effective compatibilizer for the immiscible blends of PBT and PA66. © 2000 Society of Chemical Industry     

Study on morphology and viscoelastic properties of PP/PET/SEBS ternary blend and their fibers

The morphology development of polypropylene (PP)/polyethylene terephthalate (PET)/styrene‐ethylene‐butylene‐styrene (SEBS) ternary blends and their fibers were studied by means of scanning electron microscopy (SEM) in conjunction with the melt linear viscoelastic measurements. The morphology of the blends was also predicted by using Harkin's spreading coefficient approach. The samples varying in composition with PP as the major phase and PET and SEBS as the minor phases were considered. Although SEM of the binary blends showed matrix‐dispersed type morphology, the ternary blend samples exhibited a morphological feature in which the dispersed phase formed aggregates consisting of both PET and SEBS particles distributed in the PP matrix. The SEM of the blend samples containing 30 and 40 wt % of total dispersed phase showed an agglomerated structure formed between the aggregates. The SEM of the PP/PET binary fiber blends showed long well‐oriented microfibrils of PET whereas in the ternary blends, the microfibrils were found to have lower aspect ratio with a fraction of the SEBS stuck on the microfibril fracture surfaces. These results were attributed to a core‐shell type morphology in which the PET and SEBS formed the core‐shells distributed in the matrix. The melt viscoelastic behavior of the ternary blends containing less than 30 wt % of the total dispersed phase was found to be similar to the matrix and binary blend samples whereas the samples containing 30 and 40 wt % of dispersed phases exhibited a pronounced viscosity upturn and nonterminal storage modulus in low frequency range. These results were found to be in good agreement with the morphological results. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Functionalization of polypropylene with oxazoline and reactive blending of PP with PBT in a corotating twin-screw extruder

The aim of this study was to prepare a compatibilized PP/PBT blend in a twin-screw extruder, using oxazoline-functionalized PP. First we prepared the functionalized PP (PP-g-OXA), and then we used it as a compatibilizer in the subsequent reactive blending stage. Polypropylene was successfully functionalized by ricinoloxazoline maleinate in a corotating twin-screw extruder using a melt free radical grafting technique. Grafting yields up to 2.1 phr were achieved. This functionalized PP used as a compatibilizer markedly improved the mechanical properties of the uncompatibilized PP/PBT (PBT content 30 wt %) blend. Significant improvements were observed, especially in impact strength (Charpy) and elongation at break of the compatibilized blends. The increased interactions between the phases were characterized by SEM analysis, DMTA, and DSC experiments. The properties of the blend greatly depended on the degradation of the PP during grafting. An optimal content of compatibilizer exists, which is dependent on the degradation of PP, grafting yield of oxazoline monomer, and on the amount of free, ungrafted monomer present in the compatibilizer. These factors can be adjusted by properly choosing the processing conditions and chemical parameters. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 883–894, 1997     

Improved compatibility of high‐density polyethylene/poly(ethylene terephthalate) blend by the use of blocked isocyanate group

The blocked isocyanate group (BHI) was synthesized to improve the storage stability of HI (2‐hydroxyethyl methacrylate combined with isophorone diisocyanate) and characterized by Fourier transform infrared spectroscopy (FTIR). High‐density polyethylene grafted with the blocked isocyanate group (HDPE‐g‐BHI) was used as a reactive compatibilizer for an immiscible high‐density polyethylene/poly(ethylene terephthalate) (HDPE/PET) blend. A possible reactive compatibilization mechanism is that regenerated isocyanate groups of HDPE functionalized by BHI react with the hydroxyl and carboxyl groups of PET during melt blending. The HDPE‐g‐BHI/PET blend showed the smaller size of a dispersed phase compared to the HDPE/PET blend, indicating improved compatibility between HDPE and PET. This increased compatibility was due to the formation of an in situ graft copolymer, which was confirmed by dynamic mechanical analysis. Differential scanning calorimetry (DSC) analysis represented that there were few changes in the crystallinity for the continuous PET phase of the HDPE‐g‐BHI/PET blends, compared with those of the HDPE/PET blends at the same composition. Tensile strengths and elongations at the break of the HDPE‐g‐BHI/PET blends were greater than those of the HDPE/PET blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1017–1024, 2000     

聚对苯二甲酸乙二酯/聚丙烯不相容共混体系的结构流变学

通过熔融共混制备了不相容的聚对苯二甲酸乙二醇酯（PET）/聚丙烯（PP）复合体系，研究了复合体系的结构流变学。结果表明，PET/PP共混体系的不相容相形态显著影响其稳态和动态流变行为。当PP组分为分散相时，复合体系表现出动态形状松弛;当两组分呈多种相形态共存时，复合体系表现出强烈的低频区弹性响应;而当PET组分为分散相时，复合体系的剪切敏感性则相对较小。在较高剪切应力作用下，分散相液滴的凝聚是影响体系流变行为的控制因素，而在较低的剪切应力作用下，液滴的破碎则成为控制因素。     

Blends of poly(ethylene terephthalate) and poly(butylene terephthalate)

Commercial grade poly(ethylene terephthalate), (PET, intrinsic viscosity = 0.80 dL/g) and poly(butylene terephthalate), (PBT, intrinsic viscosity = 1.00 dL/g) were melt blended over the entire composition range using a counterrotating twin‐screw extruder. The mechanical, thermal, electrical, and rheological properties of the blends were studied. All of the blends showed higher impact properties than that of PET or PBT. The 50:50 blend composition exhibited the highest impact value. Other mechanical properties also showed similar trends for blends of this composition. The addition of PBT increased the processability of PET. Differential scanning calorimetry data showed the presence of both phases. For all blends, only a single glass‐transition temperature was observed. The melting characteristics of one phase were influenced by the presence of the other. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 75–82, 2005     

Use of epoxy reactivity for compatibilization of PP/PBT and PP/LCP blends

Binary blends of a reactive ethylene-based terpolymer with polybutylene terephthalate (PBT) and with a liquid crystalline polyester (LCP) were studied to clarify the possible interactions between the blended polymers. The aim was to determine the suitability of the reactive terpolymer containing epoxy reactivity as a compatibilizer in blends of polypropylene (PP) and these two polyesters. The binary blends exhibited increased viscosity during blending, changes in the crystallization of the PBT phase, and an intimate contact between the blended polymers, which pointed to strong interactions or chemical reactions between the compatibilizer and both PBT and LCP. FTIR analysis confirmed the reaction of the epoxide and formation of new esters. Most probably the carboxyl end groups of the polyesters reacted with the epoxy group of the compatibilizer. In the second part of the work the same terpolymer was shown to act as a compatibilizer in PP/PBT and PP/LCP blends. This behavior was based on good mixing with the PP phase and on the chemical reactivity or strong interactions with the polyesters demonstrated in the investigations on binary blends. Addition of 5 wt% of the compatibilizer improved the impact strength, especially in PP/PBT blends where synergistic behavior was found at compositions of 80/20 and 20/80. In PP/LCP blends, the compatibilizer significantly improved the impact strength of unnotched samples at 20 wt % LCP content. In both blends, the compatibilizer reduced the size of the dispersed domains and caused them to attach better in the matrix. © 1995 John Wiley & Sons, Inc.     

PET/PP blending by using PP‐g‐MA synthesized by solid phase

In attempts to improve the compatibility of polypropylene (PP) with polyethylene terephthalate (PET), a maleic anhydride grafted PP (PP‐g‐MA) was evaluated as a compatibilizer in a blend of 30/70 wt % PP/PET. PP‐g‐MA was produced from isotactic homopolymer PP utilizing the technique of solid phase graft copolymerization. Qualitative confirmations of the grafting were made by Fourier transform infrared spectroscopy (FTIR). Three different weight percent of compatibilizer, PP‐g‐MA, i.e., 5, 10, and 15 wt % have been used in PP/PET blends. The compatibilizing efficiency for PP/PET blend was examined using differential scanning calorimetry (DSC), optical microscopy (OM), scanning electron microscopy (SEM) of crycrofractured surfaces, and energy dispersive X‐ray spectrum (EDAX). The results show that the grafted PP promotes a fine dispersed phase morphology, improves processability, and modifies the crystallization behavior of the polyester component. These effects are attributed to enhance phase interaction resulting in reduced interfacial tension. Also, the results show that the compatibilizing effects of the three amounts of grafted PP in blend are different and dependent on the amount used. Adding 10 wt % of compatibilizer into blend produced the finest dispersed morphology. Elemental analysis results show that PP is matrix. DSC determination revealed that the melting temperature (T_m) of the PET component declined to some extent by comparison with neat PET. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104, 3986–3993, 2007     

Poly(ethylene terephthalate)/polypropylene reactive blends through isocyanate functional group

To evaluate the compatibilization effects of an isocyanate group on poly(ethylene terephthalate)/polypropylene (PET/PP) blends through a reactive blend, PP grafted with 2‐hydroxyethyl methacrylate‐isophorone diisocyanate (PP‐g‐HI) was prepared and blended with PET. In view of the blend morphology, the presence of PP‐g‐HI reduced the particle size of the dispersed phase by the reduced interfacial tension between the PP and PET phases, indicating the in situ copolymer (PP‐g‐PET) generated during the melt blending. The DSC thermograms for the cooling run indicated that the PET crystallization in the PP‐g‐HI rich phase was affected by the chemical reactions of PET and PP‐g‐HI. The improved mechanical properties for the PET/PP‐g‐HI blends were shown in the measurement of the tensile and flexural properties. In addition, the water absorption test indicated that the PET/PP‐g‐HI blend was more effective than the PET/PP blend in improving the water resistance of PET. The positive properties of PET/PP‐g‐HI blends stemmed from the improved compatibilization of the PET/PP blend. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1056–1062, 2001     

Partially Bio-Based Polyester Bead Foams via Extrusion Foaming of Poly(butylene terephthalate)/Poly(butylene furanoate) Blends

The interest in bio-based alternatives to classical polyesters such as poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT) is steadily growing to achieve a more sustainable approach to polymer materials. In this study, PBT/poly(butylene furanoate) (PBF) blends are prepared, characterized and extrusion foamed. PBF as a bio-based polyester offers two advantages. The ecological footprint of the material is reduced, and additionally, it can be used in Diels-Alder reactions at the blend surface to support fusion of the foamed beads. The blending behavior of the polyesters is investigated using samples prepared in a microcompounder, particularly focused on the miscibility of the blends and transesterification reactions. The blends are thermodynamically immiscible but show a certain degree of transesterification according to nuclear magnetic resonance (NMR) spectroscopy. The morphology of blend beads produced by an extrusion foaming process is analyzed regarding their cell density, cell size distribution, and open-cell content. It is shown that PBF has a positive effect on the bead foam morphology. The use of a bifunctional linker designed for chemical fusion of the bead surfaces allows to obtaining of molded parts, in contrast to beads containing pure PBT.     

Melting,crystallization behaviors,and nonisothermal crystallization kinetics of PET/PTT/PBT ternary blends

The melting, crystallization behaviors, and nonisothermal crystallization kinetics of the ternary blends composed of poly(ethylene terephthalate), poly(trimethylene terephthalate) (PTT) and poly(buthylene terephthalate) (PBT) were studied with differential scanning calorimeter (DSC). PBT content in all ternary blends was settled invariably to be one‐third, which improved the melt‐crystallization temperature of the ternary blends. All of the blend compositions in amorphous state were miscible as evidenced by a single, composition‐dependent glass transition temperature (T_g) observed in DSC curves. DSC melting thermograms of different blends showed different multiple melting and crystallization peaks because of their various polymer contents. During melt‐crystallization process, three components in blends crystallized simultaneously to form mixed crystals or separated crystals depending upon their content ratio. The Avrami equation modified by Jeziorny and the Ozawa theory were employed to describe the nonisothermal crystallization process of two selected ternary blends. The results spoke that the Avrami equation was successful in describing the nonisothermal crystallization process of the ternary blends. The values of the t_1/2 and the parameters Z_c showed that the crystallization rate of the ternary blends with more poly(ethylene terephthalate) content was faster than that with the lesser one at a given cooling rate. The crystal morphology of the five ternary blends investigated by polarized optical microscopy (POM) showed different size and distortional Maltese crosses or light spots when the PTT or poly(ethylene terephthalate) component varied, suggesting that the more the PTT content, the larger crystallites formed in ternary blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Structure and property relationship of thermotropic liquid crystal polymer and polyester composite fibers

Poly(ethylene 2,6‐naphthalate) (PEN) and poly(ethylene terephthalate) (PET) composite fibers reinforced with a thermotropic liquid crystal polymer (TLCP) were prepared by the melt blending and spinning process to achieve high performance fibers with improved processability. Polymer composite fibers consisting of cheap polyester and small quantity of expensive TLCP are of interest from an economic point of view and from an industrial perspective. The increase in the birefringence and density of the TLCP/PEN/PET composite fibers with the spinning speed was attributable to the enhancement of the molecular orientation and effective packing between chains in the TLCP/PEN/PET composite fibers. Annealing process resulted in the formation of more ordered and perfect crystalline structure and higher crystallinity, improving the mechanical properties of the TLCP/PEN/PET composite fibers. The increase in the crystallite size and the degree of chain extension with increasing spinning speed resulted in the gradual increment of the long period for the TLCP/PEN/PET composite fibers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006.     

The fine structure of bicomponent polyester fibers

The application of alkaline hydrolysis to study the change in the fine structure of bicomponent polyester fibers as their surface is removed progressively was explored. The samples were prepared with a poly(butylene terephthalate) (PBT) sheath and a poly(ethylene terephthalate) (PET) core. The reagent used to hydrolyze the PBT was 1M NaOH in 75/25 methanol to water since it appeared to react topochemically with the fiber. The solution reacted more rapidly with PET than with PBT. Thus, when necessary to retard the weight loss of the bicomponent fibers, after a 2‐h hydrolysis with this reagent to remove PBT, it was replaced with aqueous 1M NaOH solution containing 0.1% cetrimmonium bromide. Unlike homofil PET or PBT fibers, where alkaline attack appeared to be confined to the surface and left the residue relatively smooth, the bicomponent fiber was attacked unevenly, and penetration to the PET core occurred before all the PBT at the surface was removed. Nevertheless, most of the reaction was confined initially to the PBT sheath. The tenacity and extension at break of the PBT–PET fiber passed through a maximum as hydrolysis progressed. The fall in tenacity at high weight losses is ascribed to increasing surface defects in the fiber surface. After removal of the PBT by the hydrolysis, the birefringence of the residue became progressively higher. The synergistic effect of the PBT sheath on the properties of the PET core and the possible causes of the nonuniform hydrolysis at the PBT surface are discussed. An equation is proposed that includes an interaction parameter, which can be utilized to determine which property is affected most by the hydrolysis of a bicomponent fiber. In this instance, it appears from the parameters that the order is strength > extension at break ≈ birefringence. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1163–1173, 1999     

裂解气相色谱质谱技术鉴定聚酯纤维

应用傅里叶变换红外光谱、裂解气相色谱质谱(PyGC-MS)联用技术鉴定聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚对苯二甲酸丙二醇酯(PTT)、聚对苯二甲酸-1,4-环己二甲醇酯(PETG)纤维。结果表明:PET,PBT,PTT,PTEG纤维可以应用红外光谱初步鉴定为聚酯纤维,但4种纤维的红外光谱类似,难以具体鉴别,而该4种纤维的PyGC-MS具有各自的特征裂解产物,其中PET,PBT,PTT的特征裂解产物分别具有100%相对丰度的苯甲酸、对苯二甲酸单丁烯酯、对苯二甲酸单丙烯酯,PETG的特征裂解产物为1,4-二亚甲基-环己烷、2,4,6-辛三烯等,以此4种聚酯特征裂解产物为鉴定PET,PBT,PTT,PTEG纤维的依据。该方法简便、快速、准确,已应用于实际检测。     

(E/VAC)-g-MAH对PP/PBT共混体系的增容改性

以过氧化苯甲酰(BPO)为引发剂,通过熔融接枝法在Brabender转矩流变仪中制得马来酸酐接枝(乙烯/乙酸乙烯酯)共聚物[(E/VAC)-g-MAH]。将该接枝物用于增容聚丙烯/聚对苯二甲酸丁二酯(PP/PBT)共混体系。结果表明,在(E/VAC)-g-MAH的作用下,PP/PBT共混物的力学性能得到提高,界面形貌得到改善,体系的相容性得到明显增强。     

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     

Study on in situ reinforcing and toughening of a semiflexible thermotropic copolyesteramide in PBT/PA66 blends

Ternary in situ composites based on poly(butylene terephthalate) (PBT), polyamide 66 (PA66), and semixflexible liquid crystalline polymer (LCP) were systematically investigated. The LCP used was an ABA30/PET liquid crystalline copolyesteramide based on 30 mol % of p‐aminobenzoic acid (ABA) and 70 mol % of poly(ethylene terephthalate) (PET). The specimens for thermal and rheological measurements were prepared by batch mixing, while samples for mechanical tests were prepared by injection molding. The results showed that the melting temperatures of the PBT and PA66 phases tend to decrease with increasing LCP addition. They also shifted toward each other due to the compatibilization of the LCP. The torque measurements showed that the ternary blends exhibited an apparent maximum near 2.5–5 wt % LCP. Thereafter, the viscosity of the blends decreased dramatically at higher LCP concentrations. Furthermore, the torque curves versus the PA66 composition showed that the binary PBT/PA66 blends can be classified as negative deviation blends (NDBs). The PBT/PA66/LCP blends containing up to 15 wt % LCP were termed as positive deviation blends (PDBs), while the blends with the LCP ≥25 wt % exhibited an NDB behavior. Finally, the tensile tests showed that the stiffness and tensile strength of ternary in situ composites were generally improved with increasing LCP content. The impact strength of ternary composites initially increased by the LCP addition, then deteriorated when the LCP content was higher than 10 wt %. The correlation between the mechanical properties and morphology of the blends is discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1975–1988, 2000     

Studies on the rheological,phase morphologic,thermal and mechanical properties of poly(trimethylene terephthalate)/ethylene propylene diene monomer copolymer grafted with maleic anhydride/metallocene polyethylene blends

The rheological, phase morphologic, thermal and mechanical properties of poly (trimethylene terephthalate)/metallocene polyethylene (PTT/mPE) blends in the presence of ethylene propylene diene monomer copolymer grafted with maleic anhydride (EPDM-g-MAH) as compatibilizer are studied by means of a capillary rheometer, scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetric analyzer (TGA). Results suggest that the compatibility of PTT/mPE blends is improved greatly after the addition of a compatibilizer. The radius of the dispersed phase in the system decreases greatly when the compatibilizer is added into the blend. When the amount of compatibilizer exceeds 8 wt-%, the size of dispersed phase becomes larger again. This phenomena could be attributed to the higher viscosity of the EPDM-g-MAH phase, which is dispersed more difficulty in the PTT phase of lower viscosity, thus the mixing efficiency is apparently decreased during the melt blending process. Moreover, the melt viscosity of the blend reaches the maximal value in case of 4 wt-% compatibilizer content, above which it would decrease again. This result is associated with the generation of more and bigger dispersed phase inside the bulk phase, thus the grafting efficiency at the interface is decreased, which could result in lower viscosity. The DSC results suggest that the mPE component shows a nucleating effect, and could increase the overall degree and rate of PTT crystallization, while the addition of a compatibilizer might slightly diminish these effects. In addition, the blend with 4 wt-% compatibilizer shows the best thermal stability. Furthermore, the Izod impact strength and the tensile strength at room temperature of the blend are also markedly improved by the addition of a 4–8 wt-% compatibilizer.     

PBT／PET共混体系相容性研究

将聚对苯二甲酸丁二醇酯(PBT)与聚对苯二甲酸乙二醇酯(PET)熔融共混,通过粘度匹配原则, 确定PBT／PET共混体系的熔体温度为275-285℃,在283℃时制得PBT／PET共混切片,并对其共混体系进行相容性研究。结果表明:PBT／PET共混体系的理论热焓均小于41．8 mJ,为热力学相容体系;由扫描电镜观察PBT／PET共混体系在PBT和PET交界处发生了相分离,当PBT与PET共混比越接近,相分离程度越明显;DSC分析表明PBT／PET共混体系在非晶区相容,晶区不相容。