Waste and Virgin LDPE/PET Blends Compatibilized with an Ethylene‐Butyl Acrylate‐Glycidyl Methacrylate (EBAGMA) Terpolymer, 1

Summary: This work is aimed at studying the morphology and the mechanical properties of blends of low density polyethylene (LDPE) and poly(ethylene terephthalate) (PET) (10, 20, and 30 wt.‐% of PET), obtained as both virgin polymers and urban plastic waste, and the effect of a terpolymer of ethylene‐butyl acrylate‐glycidyl methacrylate (EBAGMA) as a compatibilizer. LDPE and PET are blended in a single screw extruder twice; the first extrusion to homogenize the two components, and the second to improve the compatibilization degree when the EBAGMA terpolymer is applied. Scanning electron microscopy (SEM) analysis shows that the fractured surface of both the virgin polymer and the waste binary blends is characterized by a gross phase segregation morphology that leads to the formation of large PET aggregates (10–50 µm). Furthermore, a sharp decrease in the elongation at break and impact strength is observed, which denotes the brittleness of the binary blends. The addition of the EBAGMA terpolymer to the binary LDPE/PET blends reduces the size of the PET inclusions to 1–5 µm with a finer dispersion, as a result of an improvement of the interfacial adhesion strength between LDPE and PET. Consequently, increases of the tensile properties and impact strength are observed.

SEM micrographs of the fracture surface of a waste 70/30 LDPE/PET blend (R30) and of its blend with 15 pph of EBAGMA (R30C). Magnification × 1 000.     

Melt Mixing of Ethylene/Butyl Acrylate/Glycidyl Methacrylate Terpolymers with LDPE and PET

The chemical modification by melt‐mixing of an EBAGMA terpolymer with LDPE and PET was investigated with the aim to use these EBAGMA/LDPE and EBAGMA/PET blends (in equal weight quantities) as compatibilizer master batches to improve the compatibility of the LDPE/PET system. It is shown that when the EBAGMA terpolymer is melt blended with LDPE, almost 40% of the initial amount of EBAGMA is linked to the LDPE backbone. In contrast, in the case of EBAGMA/PET, FT‐IR spectra indicate the total reactivity between the two components through the reaction of the epoxy group of EBAGMA with the PET terminal groups. SEM analysis shows that both master batches present two well‐interconnected phases.

     

MAH接枝LDPE对PET/LDPE共混物增容作用的研究

本文研究了马来酸酐(MAH)在引发剂过氧化二异丙苯(DCP)存在下,与LDPE在挤出机中进行熔融接枝反应,所得接枝物GPE对PET/LDPE共混体系的增容作用.共混物的冲击强度及应力应变曲线结果表明.GPE能明显改善共混体系的相容性,提高共混体系的冲击强度,仅用20%的GPE就能使共混物由脆性断裂变为韧性断裂.利用SEM观察共混物的冲击断面形貌,结果表明,PET与LDPE完全不相容,GPE能明显改善PET与LDPE共混物的相容性,使分散相颗粒细化.而DSC结果表明:PET/LDPE/GPE与PET/LDPE一样都是热力学不相容体系,共混物存在两相结构,PET与LDPE不形成共晶.GPE在共混物中仅起相间界面相容剂的作用.     

The Use of Ethylene/Propylene Copolymers as Compatibilizers for Recycled Polyolefin Blends

Compatibilizing effects of ethylene/propylene (EPR) diblock copolymers on the morphology and mechanical properties of immiscible blends produced from recycled low‐density polyethylene (PE‐LD) and high‐density polyethylene (PE‐HD) with 20 wt.‐% of recycled poly(propylene) (PP) were investigated. Two different EPR block copolymers which differ in ethylene monomer unit content were applied to act as interfacial agents. The morphology of the studied blends was observed by scanning‐ (SEM) and transmission electron microscopy (TEM). It was found that both EPR copolymers were efficient in reducing the size of the dispersed phase and improving adhesion between PE and PP phases. Addition of 10 wt.‐% of EPR caused the formation of the interfacial layer surrounding dispersed PP particles with the occurrence of PE‐LD lamellae interpenetration into the layer. Tensile properties (elongation at yield, yield stress, elongation at break, Young's modulus) and notched impact strength were measured as a function of blend composition and chemical structure of EPR. It was found that the EPR with a higher content of ethylene monomer units was a more efficient compatibilizer, especially for the modification of PE‐LD/PP 80/20 blend. Notched impact strength and ductility were greatly improved due to the morphological changes and increased interfacial adhesion as a result of the EPR localization between the phases. No significant improvements of mechanical properties for recycled PE‐HD/PP 80/20 blend were observed by the addition of selected block copolymers.     

Reactive Compatibilizer Precursors for LDPE/PA6 Blends, 4

Summary: The effectiveness of some thermoplastic elastomers grafted with maleic anhydride (MA) or with glycidyl methacrylate (GMA) as compatibilizer precursors (CPs) for blends of low density polyethylene (LDPE) with polyamide‐6 (PA) has been studied. The CPs were produced by grafting different amounts of MA or GMA onto a styrene‐block‐(ethylene‐co‐1‐butene)‐block‐styrene copolymer (SEBS) (KRATON G 1652), either in the melt or in solution. A commercially available SEBS‐g‐MA copolymer with 1.7 wt.‐% MA (KRATON FG 1901X) was also used. The effect of the MA concentration and of other characteristics of the SEBS‐g‐MA CPs was also studied. The specific interactions between the CPs and the blends components were investigated through characterizations of the binary LDPE/CP and PA/CP blends, in the whole composition range. It was demonstrated that the SEBS‐g‐GMA copolymers display poor compatibilizing effectiveness due to cross‐linking resulting from reactions of the epoxy rings of these CPs with both the amine and the carboxyl end groups of PA. On the contrary, the compatibilizing efficiency of the MA‐grafted elastomers, as revealed by the thermal properties and the morphology of the compatibilized blends, was shown to be excellent. The results of this study confirm that the anhydride functional groups possess considerably higher efficiency, for the reactive compatibilization of LDPE/PA blends, than those of the ethylene‐acrylic acid and ethylene‐glycidyl methacrylate copolymers investigated in previous works.

SEM micrograph of the 75/25 LD08/PA blend (with 2 phr SEBSMA1).     

Environmental Stress‐Cracking Resistance of LDPE/EVA Blends

Blends of low‐density polyethylene with random copolymers of ethylene and vinyl acetate (PE/EVA) are studied with respect to their environmental stress‐cracking resistance (ESCR) using the Bell‐telephone test. This system shows the shortest time to failure in the ESCR test after annealing at 50 °C in a stress‐cracking agent (Igepal solution) compared with that in the tests conducted at 30 and 70 °C. The increase of the time to failure at 70 °C as compared with that at 50 °C is probably the result of the semicrystalline proportion of EVA melting. Transmission electron microscopy images (see Figure) reveal that EVA particles are molten and deformed in bending direction of the sample at 70 °C in contrast to samples annealed at 50 and 30 °C. TEM pictures of a failed sample during the test conducted at 50 °C indicate that EVA particles can stop crack propagation.

TEM image of PE/EVA‐5.4 after 1 000 h in ESCR test conditions at 70 °C.     

CaCO3/淀粉/LDPE复合材料流变性能研究

以活化的CaCO3和淀粉两种典型无机和有机粉体与LDPE树脂共混,通过熔融共混法制备了CaCO3/淀粉/LDPE共混物,用毛细管流变仪研究了其流变性能.结果表明CaCO3/淀粉/LDPE共混物属假塑性流体,其表观黏度随剪切速率和温度的增加而减少,随淀粉在CaCO3/淀粉/LDPE共混物中含量的增加而增加.     

辐射交联LDPE/EVA混合体系泡沫片材性能的研究

辐射交联LDPE/EVA混合体系泡沫片材表观光滑、柔软,手感好,表观密度较小,材料具有优异的力学性能,较高的拉伸强度、断裂伸长率和撕裂强度。进一步研究了产生宏观性能差异的原因是辐射交联LDPE/EVA混合体系泡沫片材制备成型工艺的特殊性,体系的交联度对制品性能影响很大。通过凝胶分析知道交联度与辐照剂量、LDPE树脂的物理性能和EVA树脂在混合体系的含量有关。此外,LDPE树脂的物理性能和EVA在混合体系的含量对材料宏观性能也有影响。     

Blends of LDPE/chitosan using epoxy‐functionalized LDPE as compatibilizer

LDPE and chitosan blends were prepared using an epoxy‐functionalized polyethylene as compatibilizing agent for improving interfacial adhesion. Compatibilization improved both tensile and flexural properties (with values approaching close to that of neat LDPE) when compared with that of uncompatibilized blends. However, the elongation at break reduced due to the addition of rigid chitosan. Thermogravimetric analysis showed a two‐stage degradation, while differential scanning calorimetry exhibited reduced crystallinity for compatibilized blends. Biodegradation studies revealed increased biodegradability with increase in chitosan loading. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Reactive compatibilization of PA6/LDPE blends with an ethylene-acrylic acid copolymer and a low molar mass bis-oxazoline

A sample of polyamide-6 (PA) was blended with low density polyethylene (LDPE) in the 80/20 wt/wt ratio, either without and with 2 phr of an ethylene-acrylic acid copolymer (EAA), Which was known to behave as a compatibilizer precursor, and the effect of the addition of small amounts (0.2 or 0.35 phr) of a fourth component, 2,2′-(1,3-phenylene)-bis(2-oxazoline) (PBO), was investigated. The reactions of PBO with EAA, PA and their blends were studied by recording as a function of time the torque applied to the blending apparatuses and by studying the solubility behavior of the products in formic acid. The PALDPE blends were prepared in a co-rotating twin screw extruder and were characterized by Molau tests, differential scanning calorimetry, scanning electron microscopy, rheology, and determination of the ultimate mechanical properties, including impact tests. The results indicate that the effectiveness of EAA as a compatibilizer precursor is considerably enhanced when PBO is added into the blends. It is thought that the reactions of PBO with the free carboxyl groups of EAA and with the amine or carboxyl end groups of PA run, at least in part, toward the formation of PA-g-EAA copolymers acting as the true compatibilizers for these blends.     

Potential role of nanofillers as compatibilizers in immiscible PLA/LDPE Blends

This article describes the use of commercial silica (SiO₂) and calcium carbonate (CaCO₃) nanofillers as compatibilizers in immiscible polylactide/low‐density polyethylene (PLA/LDPE) blends. The general aim of the study was to investigate the possibilities of replacing standard commodity plastics such as LDPE based on non‐renewable mineral oil resources with the biodegradable renewable polymer PLA in compatibilized PLA/LDPE blends for use in the packaging industry. The calculations of the minimal interfacial energy and optimal wetting abilities indicated that SiO₂ filler was a better potential compatibilizer than CaCO₃ for a given PLA/LDPE blend. This was due to its preferential localization at the interface. The significantly improved morphology of the ternary PLA/LDPE/SiO₂ blend was found to present an increased strength, toughness, and crystallinity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41414.     

Use of poly(ethylene‐co‐vinyl alcohol) as compatibilizer in LDPE/thermoplastic tapioca starch blends

Poly(ethylene‐co‐vinyl alcohol) (EVOH) was used as a compatibilizer to make blends of low‐density polyethylene (LDPE) and plasticized starch (TS). The tensile properties and impact strength were measured and compared with those of neat LDPE. The morphology of the blend specimens, both fractured and unfractured, was observed by scanning electron microscopy. Comparison of the properties showed that the impact strength of the blend improves significantly by the addition of a compatibilizer even with a high TS loading of 40 and 50% (by weight). A high elongation at break almost matching that of neat polyethylene was also obtained. The blend morphology of the etched specimens revealed fine dispersion of the starch in the polyethylene matrix, while the fracture surface morphology clearly indicate that the failure of compatibilized blends occurs mainly by the ductile mode. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3126–3134, 2002     

Co‐agent mediated functionalization of LDPE/iPP mixtures for compatibilization of WEEE‐recovered polyvinylchloride

Mixtures of low density polyethylene/isotactic polypropylene (LDPE/iPP) 80/20 w/w were functionalized in the melt by using maleic anhydride (MAH) as the functionalizing agent, 2,5‐bis(tert‐butylperoxy)‐2,5‐dimethylhexane (L101) as the peroxide initiator and butyl 3‐(2‐furyl)propenoate (BFA) as a co‐agent suitable to prevent the degradation of iPP and to promote inter‐macromolecular reactions. The use of BFA was aimed at favouring the control of radical‐induced side reactions and the formation of interfacial graft copolymers. The functionalization degree and the modification of macromolecular architecture, which were evaluated by selective solvent extractions combined with IR, DSC and SEM analyses, were modulated by varying the L101/MAH/BFA ratio in the feed. The optimized product in terms of functionalization degree value and processability was successfully tested as compatibilizer in a polyolefin/polyvinylchloride mixture, where the polyvinylchloride component resulted from the management of waste of electrical and electronic equipment (WEEE). © 2016 Society of Chemical Industry     

Synthesis and evaluation of compatibilizer based on interpenetrating polymer networks (IPN) for PET/LDPE blends

The present work considers the evaluation of recycled polymers, which are generally incompatible and are degraded during recycling with fatal consequences to their thermal and mechanical properties. Regarding this subject, the synthesis of a new compatibilizer in network form was carried out in order to counter such incompatibility. In this sense, low density polyethylene (LDPE) and poly(ethylene terephthalate) (PET) were compatibilized via the implementation of an interpenetrating polymer network (IPN), which was specifically synthesized to possess chemical groups that are akin to both plastics, PET and LDPE. The effects of the relative amount of poly(acrylic acid) (PAA) in the compatibilizer and the amount in the blends of PET/LDPE were evaluated. The results show that mechanical properties and interfacial adhesion of PET/LDPE blends were modified and improved with the addition of the synthesized compatibilizer compared with a commercial compatibilizer (polyethylene grafted with maleic anhydride, PE‐g‐AA). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43704.     

PP/PET共混体系及其合金纤维的研究

用增容剂PP-g-AA增容PP/PET共混体系。研究了增容剂含量、共混物组成、共混时间、共混温度以及螺杆转速对PP/PET相形态的影响。结果表明:增容剂的加入大大改善了PP/PET两相间的相容性,并且增容剂的添加量有一最佳值,为PET质量的50%。随着PET含量的增加,分散相的尺寸有所增加。共混温度和共混时间均有一最佳值。随着螺杆转速的提高,分散相的尺寸减小,分布趋于均一,相容性也得到改善。另外,还制备了PP/PET合金纤维,对其表面处理后以及断面SEM观察均表明分散相PET原位成纤,这些微纤提高了合金纤维的力学性能。测试了合金纤维的力学性能,发现组分比为90/10/5时,合金纤维具有最好的力学性能。     

PET-PEN共聚酯对PET/PEN共混物的增容作用及其机理

使用聚对苯二甲酸乙二酯(PET)-聚萘二甲酸乙二酯(PEN)无规共聚酯作增容剂,通过双螺杆挤出机熔融共混,制备了不同PET-PEN共聚酯用量的PET/PEN共混物,采用差示扫描量热分析、热重分析、热变形温度测试以及力学实验等方法,研究了该共混物的相容性及其它性能。结果表明,PET-PEN共聚酯对PET/PEN共混物具有明显的增容作用,能有效提高PET/PEN共混物的热稳定性,其用量越高,热稳定性提高越明显,当PET-PEN共聚酯用量为15质量份时,起始失重温度提高了20.3℃。PET-PEN共聚酯增容剂能提高PET/PEN共混物的维卡软化温度、拉伸和弯曲性能以及冲击性能,当PET-PEN共聚酯用量为5质量份时,增容改性的综合效果最好。     

mLLDPE及mLLDPE/LDPE共混物挤出加工性能的研究

使用双螺杆挤出机、单螺杆挤出机研究了mLLDPE及mLLDPE/LDPE共混物挤出表面、螺杆扭矩与喂料速度、螺杆转速之间的关系 ,并讨论了有机硅对mLLDPE/LDPE共混物挤出性能的影响     

PET/PBT共混导电复合材料的研究

采用DSC（差示扫描量热法）对PET／PBT合金的相容性进行了研究,探讨了导电炭黑加入量对PET／PBT合金的导电性能与力学性能的影响。结果表明,PET／PBT共混物在非晶区相容而在晶区不相容或部分相容,导电炭黑填充PET／PBT合金的渗流阈值为15％,导电炭黑的填充对合金的力学性能有负面的影响。     

Morphology and properties of PET/PA-6/E-44 blends

Polymer blends incorporating poly (ethylene terephthalate) (PET), polyamide-6 (PA-6), and a reactive compatibilizer (low molecular weight bisphenol-A epoxy resin—E-44) were prepared with the following E-44 weight percent concentrations: 0, 0.3, 0.6, 1, 3, 5, and 10. The samples was studied by a scanning electron microscope (SEM), a polarizing microscope (PLM), dynamic mechanical thermal analysis (DMTA), wide-angle X-ray diffraction (WAXD), a differential scanning calorimeter (DSC), infrared spectroscopy (IR), and mechanical testing. SEM and PLM showed noticeable changes in both the amorphous region and the crystalline region of the blends. The changes indicated better compatibility between the dispersed phase (PA-6) and the matrix (PET), which was further confirmed by the DMTA test. The WAXD showed that PET and PA-6 crystallized separately and no cocrystallite was found. The melting and crystallization data, obtained by DSC, suggested that the crystallization of the blend was blocked, although the hindered mechanism for the effect of E-44 on PET was different from that on PA-6. The notched impact strength and flexural strength of the PET/PA-6 blends were significantly improved when the content of E-44 was 5 wt % (improved about 500 and 400%, respectively). IR was used to study the reaction among E-44, PET, and PA-6. The result indicated that the grafting reaction and the crosslinking reaction occurred during melt blending. The obvious increase of mechanical properties and the reinforcing and toughening effect were attributed to the formation of the crosslinking net in the blend. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1505–1515, 1998     

Structural characterization of LDPE/EVA blends containing nanoclay‐flame retardant combinations

The combination of different types of organo‐modified montmorillonite (MMT) with aluminum hydroxide (aluminum trihydrate—ATH), as a flame retardant system for polyethylene‐ethylene vinyl acetate (LDPE/EVA), blends were studied. Five different types of organically modified montmorillonite clays, each with different modifier, were used. The structural characterization was carried out by X‐ray diffraction (XRD) and scanning electron microscopy in transmission mode (STEM). The mechanical and rheological properties were also evaluated. The XRD analysis showed a clear displacement of the d₀₀₁ signal, which indicates a good degree of intercalation, especially for the MMT‐I28 and MMT‐20, from Nanocor and Southern Clay Products, respectively. The presence of ATH and the compatibilizer did not have any effect on the exfoliation of the studied samples. The thermal stability and flame retardant properties were evaluated by thermogravimetric analysis (TGA), limiting oxygen index (LOI—ASTM D2863), and flammability tests (Underwriters Laboratory—UL‐94). The effect of different compatibilizers on the clay dispersion and exfoliation was studied. The results indicated that the addition of montmorillonite makes it possible to substitute part of the ATH filler content while maintaining the flame retardant requirements. The thermal stability of MMT/ATH‐filled LDPE/EVA blends presented a slight increase over the reference ATH‐filled LDPE/EVA blend. Compositions with higher clay content (10 wt %) showed better physicochemical properties. The increased stability of the higher clay content compositions results from the greater inorganic residual formation; this material has been reported to impart better performance in flammability tests. The mechanical properties and flame retardancy remained similar to those of the reference compound. The reduced ATH content resulted in lower viscosities and densities, facilitating the processing of the polymer/ATH/clay compounds. Extrusion of these compounds produced a lower pressure in the extrusion head and required reduced electrical power consumption. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011