Comparison of olefin copolymers as compatibilizers for polypropylene and high‐density polyethylene

Some polyolefin elastomers were compared as compatibilizers for blends of polypropylene (PP) with 30 wt % high‐density polyethylene (HDPE). The compatibilizers included a multiblock ethylene–octene copolymer (OBC), two statistical ethylene–octene copolymers (EO), two propylene–ethylene copolymers (P/E), and a styrenic block copolymer (SBC). Examination of the blend morphology by AFM showed that the compatibilizer was preferentially located at the interface between the PP matrix and the dispersed HDPE particles. The brittle‐to‐ductile (BD) transition was determined from the temperature dependence of the blend toughness, which was taken as the area under the stress–strain curve. All the compatibilized blends had lower BD temperature than PP. However, the blend compatibilized with OBC had the best combination of low BD temperature and high toughness. Examination of the deformed blends by scanning electron microscopy revealed that in the best blends, the compatibilizer provided sufficient interfacial adhesion so that the HDPE domains were able to yield and draw along with the PP matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Epitaxial crystallization of olefin block copolymers (OBCs) on uniaxially oriented isotactic polypropylene and high-density polyethylene films

The epitaxial crystallization behavior of olefin block copolymers (OBCs) on uniaxially oriented isotactic polypropylene (iPP) and high-density polyethylene (HDPE) films has been investigated by transmission electron microscopy (TEM). The crystallizable blocks of the OBCs under investigation were epitaxially nucleated by both iPP and HDPE substrates and epitaxial growth of OBC lamellae was observed. Epitaxial crystallization of the OBCs has been found for slow and fast cooling conditions from the melt which pointed to the strong interaction between the polyolefin substrates and the OBCs. However, the epitaxial morphology of the OBCs strongly depends on their octene concentration difference (Δ_C8) between crystallizable and non-crystallizable blocks, which probably is related to the OBC segregation strength in the melt. With high Δ_C8 the development of epitaxial crystallization of the OBC was restricted within isolated crystalline domains surrounded by the amorphous phase. In contrast, with low Δ_C8 the oriented lamellae of the OBC were distributed homogeneously on iPP but formed separated crystalline domains on HDPE, which has a stronger nucleation capability than iPP on the crystalline OBC blocks because of its similar molecular architecture. Our study points to epitaxy as another reason for the strong interaction between OBC and polyolefins which causes the advanced compatibilization behavior of OBCs when compared with conventional random copolymers.     

PP/OBC/EPDM-g-MAH复合材料的制备及性能

以聚丙烯(PP)为基体材料,乙烯-辛烯嵌段共聚物(OBC)为增韧材料,三元乙丙橡胶接枝马来酸酐共聚物(EPDM-g-MAH)为相容剂,制备了PP/OBC/EPDM-g-MAH复合材料。用DSC、SEM、转矩流变仪分析了OBC及EPDM-g-MAH对PP结晶性能、断面相结构、流变性能的影响,测试了复合材料的力学性能。结果表明:加入15%OBC,PP/OBC复合材料的熔融温度升高了1.63℃,结晶度降低了5.4%,断裂伸长率及缺口冲击强度明显提高,弯曲强度和拉伸强度有所下降;含4%EPDM-g-MAH的PP/OBC/EPDM-g-MAH复合材料,OBC粒子均匀分散在PP基体中,粒径明显细化,熔融塑化扭矩值降低,结晶速率加快;与纯PP相比,断裂伸长率和缺口冲击强度分别提高了128.57%和107.96%,柔韧性有较大幅度提高。     

Effect of tie-layer thickness on the adhesion of ethylene-octene copolymers to polypropylene

The adhesion of some ethylene-octene copolymers to polypropylene (PP) and high density polyethylene (HDPE) was studied in order to evaluate their suitability as compatibilizers for PP/HDPE blends. A one-dimensional model of the compatibilized blend was fabricated by layer-multiplying coextrusion. The microlayered tapes consisted of many alternating layers of PP and HDPE with a thin tie-layer inserted at each interface. The thickness of the tie-layer varied from 0.1 to 15 μm, which included thicknesses comparable to those of the interfacial layer in a compatibilized blend. The delamination toughness was measured in the T-peel test. Generally, delamination toughness decreased as the tie-layer became thinner with a stronger dependence for tie layers thinner than 2 μm. Inspection of the crack-tip damage zone revealed a change from a continuous yielded zone in thicker tie layers to a highly fibrillated zone in thinner tie layers. By treating the damage zone as an Irwin plastic zone, it was demonstrated that a critical stress controlled the delamination toughness. The temperature dependence of the delamination toughness was also measured. A blocky copolymer (OBC) consistently exhibited better adhesion to PP than statistical copolymers (EO). A one-to-one correlation between the delamination toughness and the reported performance of the copolymers as compatibilizers for PP/HDPE blends confirmed the key role of interfacial adhesion in blend compatibilization.     

PP／HDPE／SBS三元共混物的研究——形态结构与性能

研究了PP/HDPE/SBS三元共混物的性能及形态结构特征。研究结果表明,PP三元共混物的冲击韧性除与SBS的含量密切相关外,还与HDPE的含量有关,HDPE起到了与SBS相似的增韧作用。由于HDPE的掺入,减少了SBS的含量,制成了一种力学性能均衡的超高韧性PP三元共混材料。形态结构的研究表明,共混物中,SBS呈颗粒状分布,另外SBS还与HDPE组成了具有包藏结构的复合粒子。     

粉状聚丙烯增韧增强研究

采用机械共混方法对粉状聚丙烯（PP）进行了增韧增强研究，探讨了增韧剂、增强剂和有少量自制的固相甲基丙烯酸（MAA）接枝粉状聚丙烯（PP-g-MAA)作增容剂存在下对粉状PP共混体系力学性能的影响，用热重分析法考察了改性粉状PP的热性能。结果表明，（乙烯／丙烯／二烯）共聚物（EPDM）／高密度聚乙烯（HDPE）为复合增韧剂，具有协同作用，可显著提高共混物的冲击强度：PP-g-MAA能明显改善PP／玻纤两相的界面结合力；PP／EPDM／HDPE玻璃纤维共混体系可以获得理想的增韧增强效果。     

Development of isotropic compatible HDPE/PP blends for structural applications

In an attempt to provide superior products for the structural applications, this study aimed at preparing isotropic compatible high density polyethylene (HDPE)/ polypropylene (PP) blends without the use of the expensive compatibilization technique. Morphological and structural characterizations of the homopolymers and blends were carried out. In addition, some of the structurally important mechanical and thermal properties were characterized. Such characterizations were performed to investigate whether or not the blends are compatible and therefore acceptable for the structural applications. Scanning electron microscope (SEM) micrographs of the blend samples indicate that the interfacial adhesion between HDPE and PP phases is intimate in the 5/95 HDPE‐PP, good in the 85/15 HDPE‐PP and 95/5 HDPE‐PP, fair in the 30/70 HDPE‐PP and very poor in the 50/50 HDPE‐PP. Similarly, mechanical and thermal responses of the first three blends are remarkable. The 30/70 HDPE‐PP blend displays a fairly good performance. Whereas, the properties of the 50/50 HDPE‐PP blend are very poor. This decides that the first three blends are compatible and, therefore, structurally attractive materials. The fourth is partially compatible and, as a consequence, can be rather acceptable for the structural applications. However, the fifth is incompatible and, of course, is not acceptable for such applications. On the other hand, SEM micrographs and differential scanning calorimetry results indicate that the crystalline structures of individual polymers are appreciably affected by blending. Additionally, the study reveals that the end use performance of blends is strongly dependent on the crystalline structure changes occurring in each component due to blending as well as the compatibility between the blend components. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Modification of PP/HDPE blends by PP-PE sequential polymerization product

The morphology and mechanical properties of polypropylene/high-density polyethylene (PP/HDPE) blends in a wide range of compositions modified by a sequential Ziegler-Natta polymerization product (PP-PE) have been investigated. PP-PE contains multiple components such as PP, ethylene-propylene copolymer (EPC), and high molecular weight polyethylene (HMWPE). The effects of PP-PE on the mechanical properties and morphology of the PP/HDPE blends are the aggregative results of all its individual components. Addition of PP-PE to the blends not only improved the tensile strength of the blends, but the elongation at break increased linearly while the moduli were nearly unchanged. Morphological studies show that the adhesion between the two phases in all the blends of different compositions is enhanced and the dispersed domain sizes of the blends are reduced monotonously with the increment of the content of PP-PE. PP-PE has been demonstrated to be a more effective compatibilizer than EPC. Based on these results, it can be concluded that the tensile strength of the blends most on the adhesion between the two phases and the elongation at break depends most on the domain size of the dispersed component. © 1995 John Wiley & Sons, Inc.     

Evaluation of olefinic block copolymer blends with amorphous polyolefins—effect of different unsaturated and saturated hydrocarbon tackifier resins on blend miscibility

Blends of ethylene–octene based olefinic block copolymer (OBC) with two amorphous polyolefin (APO) polymers [atactic propylene homopolymer (PP) and ethylene–propylene copolymer (PE–PP)] were evaluated at three different ratios. Dynamic mechanical analysis (DMA) and transmission electron microscopy (TEM) evaluations were performed to determine the blend miscibility characteristics. Viscoelastic properties of both OBC blends with PP polymer, and OBC blends with PE–PP copolymer showed incompatibility. Analysis revealed that both blends formed two phase morphologies. The effect of three unsaturated aliphatic hydrocarbon resins with varying aromatic content and two saturated hydrocarbon resins with different chemistries were evaluated as compatibilizing agent for OBC/PP and OBC/PE–PP blends. A 1 : 1 polymer blend ratio of OBC/PP and OBC/PE–PP was selected to better understand the influence of resin addition at three different levels 20, 30, and 40 wt %. The fully aliphatic unsaturated resin seems to improve the miscibility of the OBC/PP blends at higher resin addition levels, but reduced the miscibility as the aromatic content of the resin increases. However, OBC/PE–PP blends showed improved miscibility with increasing aromatic content. A ternary phase morphology was particularly observed for both OBC/PP and OBC/PE–PP blends with highly aromatic (14%) unsaturated hydrocarbon resin, in which OBC formed the continuous phase, and PP, PE–PP, and unsaturated hydrocarbon resins formed the dispersed phase. Interestingly, we did not observe much difference in miscibility characteristics between the two saturated resin chemistries in both blend systems (OBC/PP and OBC/PE–PP). The Harkins spreading coefficient concept was used to better understand the ternary blend dispersed phase morphology. Spreading coefficients indicate that the free hydrocarbon resins (both unsaturated and saturated) were encapsulated by the amorphous PP or amorphous PE–PP polymer in the dispersed phase for the respective blend compositions. Overall OBC–PP and OBC/PE–PP blends showed better miscibility characteristics with both saturated aliphatic hydrocarbon resins, irrespective of the difference in resin chemistries. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2624–2644, 2013     

i-PP/HDPE blends. III. Characterization and compatibilization at lower i-PP contents

The mechanical properties of high-density polyethylene (HDPE)-rich i-PP/HDPE blends were studied. Two grades of HDPE were investigated, one with a melt viscosity close to that of the polypropylene (PP) and the other having a much lower melt viscosity. Compatibilization of the 10/90 i-PP/HDPE blend with three copolymers (an ethylene/propylene/diene [EPDM] copolymer and two ethylene/vinylacetate [EVA] copolymers, differing in their VA content) was also investigated. Blends of PP with the low melt viscosity HDPE displayed poor mechanical properties. It was not possible to improve these properties sufficiently with EPDM or EVA. In the case where viscosity matching was achieved between PP and HDPE, addition of i-PP (up to 30%) to HDPE resulted in a large drop in the impact strength of the blends, compared to that of the neat HDPE. A large drop (>50%) was also observed in the ultimate tensile elongation. However, the flexural modulus, yield stress, and ultimate tensile strength all increased with the introduction of i-PP into HDPE. Modification of these blends with an EPDM resulted in the return of all properties to values very close to those of the neat HDPE. The ultimate tensile elongation of the EPDM-modified i-PP/HDPE blend even exceeded that of the virgin HDPE. It was also found that although EVAs can be used to compatibilize these blends these additives were not as effective as was the EPDM. © 1996 John Wiley & Sons, Inc.     

聚醚钛酸酯合成及其对聚烯烃/CaCO_3力学性能影响

将一定比例聚醚和异辛醇相混合,采用传统的Moor等反应方法制得了具有不同相对分子质量的聚醚基异辛基焦磷酸酯,再与钛酸异丙酯反应,获得异丙基三(聚醚基异辛基焦磷酰氧基)钛酸酯。经此偶联剂处理的CaCO3对于HDPE/CaCO3和PP/POE/CaCO3材料具有明显增韧、增强作用。对PVC/CPE/DOP/CaCO3材料也具有明显改善韧性的作用。经SEM测定表明,经此偶联剂处理的CaCO3与聚合物基体间的界面较模糊。偶联剂中聚醚取代基的相对分子质量和合成原料中聚醚与异辛醇的比例对材料增韧效果具有重要影响。     

Effect of ethylene-propylene copolymer with residual PE crystallinity on mechanical properties and morphology of PP/HDPE blends

Morphology and mechanical properties of polypropylene (PP)/high density polyethylene (HDPE) blends modified by ethylene-propylene copolymers (EPC) with residual PE crystallinity were investigated. The EPC showed different interfacial behavior in PP/HDPE blends of different compositions. A 25/75 blend of PP/HDPE (weight ratio) showed improved tensile strength and elongation at break at low EPC content (5 wt %). For the PP/HDPE = 50/50 blend, the presence of the EPC component tended to make the PP dispresed phase structure transform into a cocontinuous one, probably caused by improved viscosity matching of the two components. Both tensile strength and elongation at break were improved at EPC content of 5 wt %. For PP/HDPE 75/25 blends, the much smaller dispersed HDPE phase and significantly improved elongation at break resulted from compatibilization by EPC copolymers. © 1995 John Wiley & Sons, Inc.     

Relationship between cell morphology and impact strength of microcellular foamed high‐density polyethylene/polypropylene blends

Polymer blends, such as those resulting from recycling postconsumer plastics, often have poor mechanical properties. Microcellular foams have been shown to have the potential to improve properties, and permit higher‐value uses of mixed polymer streams. In this study, the effects of microcellular batch processing conditions (foaming time and temperature) and HDPE/PP blend compositions on the cell morphology (the average cell size and cell‐population density) and impact strength were studied. Optical microscopy was used to investigate the miscibility and crystalline morphology of the HDPE/PP blends. Pure HDPE and PP did not foam well at any processing conditions. Blending facilitated the formation of microcellular structures in polyolefins because of the poorly bonded interfaces of immiscible HDPE/PP blends, which favored cell nucleation. The experimental results indicated that well‐developed microcellular structures are produced in HDPE/PP blends at ratios of 50:50 and 30:70. The cell morphology had a strong relationship with the impact strength of foamed samples. Improvement in impact strength was associated with well‐developed microcellular morphology. Polym. Eng. Sci. 44:1551–1560, 2004. © 2004 Society of Plastics Engineers.     

聚烯烃改性PET的研究

通过PET与PP、HDPE、EPDM挤出共混，注射模塑制得试样。经DTA、SEM和力学性能测试，表征了共混体系的热行为、结构形态和力学性能。结果表明，在PET/PP(EPDM、HDPE)共混体系中，加入少量的PP-g-MI(EPDM-g-MAH、PE-g-MI)，可较好地改善PEt与PP(EPDM、HDPE)之间的相容性，使分散相在PET基体连续相中分散均匀，分散相尺寸减小，增加了两相间界面的粘结力；同时对PET的结晶有较强的促进作用，使其冷结晶温度降低，改善了PET的加工性能；并且能大幅度提高共混物的冲击强度。     

Structure and properties of polypropylene/high‐density polyethylene blends by solid equal channel angular extrusion

The solid equal channel angular extrusion (ECAE) process on polypropylene (PP)/high‐density polyethylene (HDPE) blends was carried out. Scanning electron microscopy (SEM) was used to observe the sample structures. Results showed that ECAE process could make PP/HDPE blends to produce orientation structure. Impact performance of ECAE‐PP/HDPE samples after ECAE process improved remarkably, especially for ECAE‐PP/HDPE (90/10)‐O whose impact strength reached 91.91 kJ/m², 18.1 times higher than that of pure PP and 11.2 times higher than that of PP/HDPE (90/10). The mechanism of enhancing between HDPE and PP was discussed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39759.     

绢英粉填充改性聚丙烯的研究

制备绢英粉填充聚丙烯共混材料 ,研究了绢英粉的粒度和处理方法对共混物力学性能的影响。通过 SEM、DSC、GPC、TMA和 MI的测定研究了绢英粉填充聚丙烯共混材料的组分变化和形态结构对其力学性能的影响。初步探讨了聚丙烯 /绢英粉共混材料的耐紫外老化性能。利用微波辐照处理聚丙烯 /绢英粉共混物改善了界面粘合性 ,提高了材料的抗冲击强度     

挤出共混中的高剪切应力对PP-HDPE-滑石粉共混材料力学性能的影响

采用提高双螺杆挤出机螺杆转速的方法,研究了双螺杆挤出机的高剪切应力作用对聚丙烯(PP)、PP-滑石粉和PP-高密度聚乙烯(HDPE)-滑石粉共混材料力学性能的影响.结果表明:双螺杆挤出机的高螺杆转速、高剪切应力作用,可促进材料中滑石粉颗粒的均匀分散、促进HDPE均匀分散于PP基体的乙丙共聚物的相态之中,可引起PP或HDPE的断链反应、引起HDPE大分子自由基与PP基体中的EPR相以及与滑石粉表面偶联助剂之间的结合反应,引起共混材料缺口冲击强度的显著增大;少量极性烯类单体的加入和较低的挤出反应温度条件(180℃)有利于形成的大分子自由基与极性烯类单体的接枝、嵌段反应、界面间的偶联结合反应及其原位增粘作用,并引起PP-HDPE-滑石粉共混材料缺口冲击强度的进一步增大.     

Effects of the viscosity ratio on polyolefin ternary blends

Polyolefin binary and ternary blends were prepared from polypropylene (PP), an ethylene–α‐olefin copolymer (mPE), and high‐density polyethylene (HDPE) on the basis of the viscosity ratio of the dispersed phase to the continuous phase. In PP/mPE/HDPE blends, fibrils were observed when the dispersed‐phase (mPE/HDPE) viscosity was less than that of PP, or when the viscosity of mPE was less than that of PP, although the viscosity of mPE/HDPE was greater than that of PP. The notched impact strength and mechanical properties such as the yield strength, flexural modulus, and hardness of PP/mPE binary blends further increased with the addition of HDPE according to the type of HDPE. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 4027–4036, 2004     

Structure and properties of PP/POE/HDPE blends

This work was aimed to counteract the effect of ethylene‐α‐olefin copolymers (POE) by reinforcing the polypropylene (PP)/POE blends with high density polyethylene (HDPE) particles and, thus, achieved a balance between toughness and strength for the PP/POE/HDPE blends. The results showed that addition of HDPE resulted in an increasing wide stress plateau and more ductile fracture behavior. With the increase of HDPE content, the elongation at break of the blends increased rapidly without obvious decrease of yield strength and Young's modulus, and the notched izod impact strength of the blends can reach as high as 63 kJ/m² at 20 wt % HDPE loading. The storage modulus of PP blends increased and the glass transition temperature of each component of the blends shifted close to each other when HDPE was added. The crystallization of HDPE phase led to an increase of the total crystallinity of the blend. With increasing HDPE content, the dispersed POE particle size was obviously decreased, and the interparticle distance was effectively reduced and the blend rearranged into much more and obvious core‐shell structure. The fracture surface also changed from irregular striation to the regularly distant striations, displaying much obvious character of tough fracture. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Compatibilization effects of block copolymers in high density polyethylene/syndiotactic polystyrene blends

Three triblock copolymers of poly[styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS) of different molecular weights and one diblock copolymer of poly[styrene-b-(ethylene-co-butylene)] (SEB) were used to compatibilize high density polyethylene/syndiotactic polystyrene (HDPE/sPS, 80/20) blend. Morphology observation showed that phase size of the dispersed sPS particles was significantly reduced on addition of all the four copolymers and the interfacial adhesion between the two phases was dramatically enhanced. Tensile strength of the blends increased at lower copolymer content but decreased with increasing copolymer content. The elongation at break of the blends improved and sharply increased with increments of the copolymers. Drop in modulus of the blend was observed on addition of the rubbery copolymers. The mechanical performance of the modified blends is strikingly dependent not only on the interfacial activity of the copolymers but also on the mechanical properties of the copolymers, particularly at the high copolymer concentration. Addition of compatibilizers to HDPE/sPS blend resulted in a significant reduction in crystallinity of both HDPE and sPS. Measurements of Vicat softening temperature of the HDPE/sPS blends show that heat resistance of HDPE is greatly improved upon incorporation of 20 wt% sPS.