Effect of reactive compatibilisation on the phase morphology and tensile properties of PA12/PP blends

Both uncompatibilized and compatibilized blends based on polyamide 12 (PA12) and isotactic polypropylene (PP) were prepared in a Brabender Plastograph®. The compatibiliser used was maleic anhydride functionalized polypropylene (PP‐g‐MA). Phase morphology of the blends was inspected in scanning electron microscope (SEM) on cryogenically fractured etched surfaces of the specimens. PA12/PP blends possessed a nonuniform and unstable morphology owing to the incompatibility between their constituents. Addition of compatibiliser improved the interfacial characteristics of the blends by retarding the rate of coalescence. So, the phase morphology became more fine, uniform, and stable. Tensile properties of both uncompatibilized and compatibilized blends were measured as a function of blend composition and compatibiliser concentration. Uncompatibilized blends displayed inferior mechanical properties to compatibilized ones; especially for those containing 40–60 wt % of PP. Reactive compatibilisation of blends was found to be efficient and improved the tensile strength of the blends considerably. Addition of PP‐g‐MA improved the interfacial adhesion, decreased the interfacial tension, and thereby, enhanced the tensile strength by 85%. Finally, various models were adopted to describe the tensile strength of the blends. The experimental data exhibited a reasonably good fit with Nielsen's first power law model. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

PP-g-GMA的制备及其增容PP/PA6共混物的性能

通过熔融接枝反应制备了甲基丙烯酸缩水甘油酯接枝聚丙烯（PP-g-GMA）,并将其作为聚丙烯/聚酰胺6（PP/PA6）共混物的相容剂,研究了PP-g-GMA对PP/PA6共混物的力学性能及形态结构的影响。结果表明,采用滴定法测得PP-g-GMA接枝率为3.35 %;当PP-g-GMA的添加量为4 %（质量分数,下同）和8 %时,PP/PA6/PP-g-GMA共混物的拉伸强度和缺口冲击强度分别较PP/PA6共混物提高了32.4 %和60.4 %;PP-g-GMA显著改善了PP/PA6 共混物的界面相容性,是PP/PA6共混物的有效增容剂。     

Compatibilization and morphology development of immiscible ternary polymer blends

We report a novel and effective strategy that compatibilizes three immiscible polymers, polyolefins, styrene polymers, and engineering plastics, achieved by using a polyolefin-based multi-phase compatibilizer. Compatibilizing effect and morphology development are investigated in a model ternary immiscible polymer blends consisting of polypropylene (PP)/polystyrene(PS)/polyamide(PA6) and a multi-phase compatibilizer (PP-g-(MAH-co-St) as prepared by maleic anhydride (MAH) and styrene (St) dual monomers melt grafting PP. Scanning electron microscopy (SEM) results indicate that, as a multi-phase compatibilizer, PP-g-(MAH-co-St) shows effective compatibilization in the PP/PS/PA6 blends. The particle size of both PS and PA6 is greatly decreased due to the addition of multi-phase compatibilizer, while the interfacial adhesion in immiscible pairs is increased. This good compatibilizing effect is promising for developing a new, technologically attractive method for achieving compatibilization of immiscible multi-component polymer blends as well as for recycling and reusing of such blends. For phase morphology development, the morphology of PP/PS/PA6 (70/15/15) uncompatibilized blend reveals that the blend is constituted from PP matrix in which are dispersed composite droplets of PA6 core encapsulated by PS phase. Whereas, the compatibilized blend shows the three components strongly interact with each other, i.e. multi-phase compatibilizer has good compatibilization between the various immiscible pairs. For the 40/30/30 blend, the morphology changed from a three-phase co-continuous morphology (uncompatibilized) to the dispersed droplets of PA6 and PS in the PP matrix (compatibilized).     

Novel approach for the preparation of a compatibilized blend of nylon 11 and polypropylene with polyhydroxybutyrate: Mechanical,thermal, and barrier properties

This article comprises of the interaction in the immiscible polymer system of nylon 11 (PA 11), polypropylene (PP), and polyhydroxybutyrate (PHB). Reactive compatibilization extrusion method with maleic anhydride-grafted polypropylene (PP-g-MA) is used to achieve compatibility within the polymer. To further improve the interaction of the blend at interphase, PHB was added as a dispersive phase in a concentration varying from 10 to 40% of the total batch. Addition of PHB motives the excellent dispersion of PP chain in PA 11 and assures the compatibility between the phases of PA 11 and PP-g-MA. The entire system of tertiary and binary phases was blended in a twin-screw extruder at different composition. The macro-optimal tensile strength, Young's modulus, bending strength, and notched impact strength of PA11/PP systems were found to be superior as compared to their noncompatibilized systems. The degradation temperature of the blends of PA11/PP and PA11/PHB/PP with and without compatibilizer was evaluated by thermogravimetric analysis (TGA). It was found that the high temperature of degradation was required for compatibilized ternary blend than that of the compatibilized binary blend. The distortion temperature of the systems was studied with the help of heat deflection temperature (HDT) and found to be advanced for blend having a higher concentration of the dispersed phase. Differential scanning calorimetry (DSC) was used to determine the % crystallinity, melting, and crystallization temperature of this system. Chemical resistance and barrier properties of the different compatibilized and noncompatibilized blends were studied. PHB dispersed phase with a reactive compatibilizer cause enhancement in chemical resistance and barrier properties of the blend. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48152.     

Compatibilization of polypropylene/nylon 6 blends with a polypropylene solid‐phase graft

The compatibilization of polypropylene (PP)/nylon 6 (PA6) blends with a new PP solid‐phase graft copolymer (gPP) was systematically studied. gPP improved the compatibility of PP/PA6 blends efficiently. Because of the reaction between the reactive groups of gPP and the NH₂ end groups of PA6, a PP‐g‐PA6 copolymer was formed as a compatibilizer in the vicinity of the interfaces during the melting extrusion of gPP and PA6. The tensile strength and impact strength of the compatibilized PP/PA6 blends obviously increased in comparison with those of the PP/PA6 mechanical blends, and the amount of gPP and the content of the third monomer during the preparation of gPP affected the mechanical properties of the compatibilized blends. Scanning electron microscopy and transmission electron microscopy indicated that the particle sizes of the dispersed phases of the compatibilized PP/PA6 blends became smaller and that the interfaces became more indistinct in comparison with the mechanical blends. The microcrystal size of PA6 and the crystallinity of the two components of the PP/PA6 blends decreased after compatibilization with gPP. The compatibilized PP/PA6 blends possessed higher pseudoplasticity, melt viscosity, and flow activation energy. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 420–427, 2004     

Influence of coalescence and interfacial tension on the morphology of PP/HDPE compatibilized blends

In this paper, the compatibilization of polypropylene (PP)/high-density polyethylene (HDPE) blend was studied through morphological and interfacial tension analysis. Three types of compatibilizers were tested: ethylene-propylene-diene copolymer (EPDM), ethylene-vinylacetate copolymer (EVA) and styrene-ethylene/butylene-styrene triblock copolymer (SEBS). The morphology of the blends was studied by scanning electron microscopy. The interfacial tension between the components of the blends was evaluated using small amplitude oscillatory shear analysis. Emulsion curves relating the average radius of the dispersed phase and the interfacial tension to the compatibilizer concentration added to the blend were obtained. It was shown that EPDM was more efficient as an emulsifier for PP/HDPE blend than EVA or SEBS. The relative role of interfacial tension reduction and coalescence reduction to particle size reduction was also addressed. It was observed that the role of coalescence reduction is small, mainly for PP/HDPE (90/10) blends compatibilized by EPDM, EVA or SEBS. The results indicated that the role of coalescence reduction to particle size reduction is lower for blends for which interfacial tension between its components is low at compatibilizer saturation.     

Acrylonitrile–butadiene–styrene toughened nylon 6: The influences of compatibilizer on morphology and impact properties

Polymer alloys have been used as an alternative to obtain polymeric materials with unique physical properties. Generally, the polymer mixture is incompatible, which makes it necessary to use a compatibilizer to improve the interfacial adhesion. Nylon 6 (PA6) is an attractive polymer to use in engineering applications, but it has processing instability and relatively low notched impact strength. In this study, the acrylonitrile–butadiene–styrene (ABS) triblock copolymer was used as an impact modifier for PA6. Poly(methyl methacrylate‐co‐maleic anyhydride) (MMA‐MA) and poly(methyl methacrylate‐co‐glycidyl methacrylate) (MMA‐GMA) were used as compatibilizers for this blend. The morphology and impact strength of the blends were evaluated as a function of blend composition and the presence of compatibilizers. The blends compatibilized with maleated copolymer exhibited an impact strength up to 800 J/m and a morphology with ABS domains more efi8ciently dispersed. Moderate amounts of MA functionality in the compatibilizer (～5%) and small amounts of compatibilizer in the blend (～5%) appear sufficient to improve the impact properties and ABS dispersion. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 842–847, 2003     

PP/EVOH/PA6共混物的性能研究

以聚丙烯接枝马来酸酐(PP-g-MAH)为相容剂,制备了聚丙烯(PP)/乙烯-乙烯醇共聚物(EVOH/)聚酰胺6(PA6)共混物,研究了PP/EVOH/PA6三元共混物的相容性、流变性能、阻隔性能、力学性能、热性能及形态结构。结果表明:相容剂与EVOH和PA6间发生了反应,提高了共混物的相容性;相容剂的加入提高了PP、EVOH、PA6的结晶温度,增强了PP与EVOH和PA6间的黏合力,降低了界面张力;EVOH占EVOH/PA6总量68%的三元共混物吸油率最小,当相容剂用量为5份时,PP/EVOH/PA6三元共混物吸油率比PP/EVOH二元共混物降低了8%。     

Enhancement of the tensile retraction properties of a styrenic block copolymer by melt blending with PA6

Styrene–ethylene‐propylene–styrene triblock copolymer (SEPS), a thermoplastic elastomer (TPE) was blended with polyamide‐6 (PA6) in an attempt to improve the retraction properties of the TPE. A maximum loading of 30 wt % of polyamide was incorporated into SEPS using twin‐screw compounding. Various reactive compatibilisers were also incorporated at a maximum loading of 10 wt %. The blends were evaluated in terms of their tensile, dynamic mechanical, and rheological behavior. Design of experiments (DOE) was used to study the effect of blending variables on the tensile properties of the blends. Complex interactions between these variables were identified using this approach. It was shown that by incorporating PA6 into SEPS, in conjunction with a compatibilizer, blends with superior retraction properties and increased tensile strength could be obtained. A mean hysteresis of 54.2 ± 0.7% was recorded for a blend containing 5 wt % PA6 and 4 wt % compatibilizer compared to 58.5 ± 0.5% for virgin SEPS. The tensile strength of this blend was almost 75% higher than virgin SEPS. Further evidence of the benefit of incorporating a reactive compatibilizer was the absence of a distinct polyamide relaxation in the dynamic mechanical thermograms for the compatibilized blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Real time assessment of the compatibilization of polypropylene/polyamide 6 blends during extrusion

The reactivity of maleic anhydride and acrylic acid polypropylene graft copolymers with amine groups and their effect in the compatibilization of polymer blends was analyzed in real time during the reactive processing of compatilized polypropylene/polyamide 6 (PP/PA6) blends. The presence of compatibilizers in the blend produces a block copolymer PP‐PA6, which stays in the blends interface, lowering the interfacial tension and reducing the PA6 particle size, affecting the light extinction phenomena. The in‐line optical detector is able to indirectly quantify the conversion of the compatibilization reaction of the blends. The signal intensity of the detector increases with the increase of the PA6 content due to the increase in the number of particles. Quantitative off‐line FTIR analyses of the compatibilized blends have shown that the amount of block copolymer formed when polypropylene grafted with acrylic acid (PP‐g‐AA) is used as compatibilizer increases with its content in the blend. There is a good correlation between the in‐line optical measurement and the off‐line amidic bond content formed. Non‐reacted compatibilizers are always present in the reactive blends whose content is proportional to its initial concentration. The PA6 particle size data obtained from scanning electron microscopy analysis showed good correlation with the in‐line measurements. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Crystallization and melting behavior of polypropylene in β-PP/polyamide 6 blends containing PP-g-MA

In this research, we used a twin-screw extruder to melt and blend PP-g-MA compatibilizer with β-polypropylene (PP)/polyamide 6 (PA6). The influences of the PA6 and PP-g-MA contents in PP/PA6 blends on crystallization and melting behavior of PP phase and morphology were investigated. The results showed that, when PP-g-MA copolymer was added to the β form of nucleated PP/PA6 blends, the anhydride groups in PP-g-MA and PA6 terminal amine groups react to form PP-g-PA graft copolymer in a two-phase interface. This reduces the interfacial tension, improves the interfacial adhesion, and reduces the size of PA6 domains in the blend. The generated PP-g-PA graft copolymer wrapped PA6 phase and buried the anhydride groups of PP-g-MA. When the proportion of PP-g-MA and PA6 was between 0.5 and 0.75, there was no longer interfering to the formation of β-crystals in the PP phase. The content of β-crystal of PP phase in blends was found to reach as large as 85.9%.     

Compatibilizers for thermotropic liquid crystalline polymer/polyethylene blends prepared by reactive mixing

This paper describes the effects of composition and processing conditions on the efficiency of the compatibilizer prepared from a thermotropic liquid crystalline polymer (TLCP) and the sodium salt of a poly(ethylene‐co‐r‐acrylic acid) ionomer (EAA‐Na) in TLCP/low‐density polyethylene (LDPE) blends and TLCP/high‐density polyethylene (HDPE) blends. The TLCP‐ionomer graft copolymer formed by a melt acidolysis reaction effectively reduced the interfacial tension between TLCP and polyethylene, which improved impact strength and toughness of the compatibilized blends. Higher processing temperatures for the reactive extrusion produced a more efficient compatibilizer, presumably due to increased graft‐copolymer formation, but the reaction temperature had little effect on the impact strength of compatibilized blends for temperatures above 300°C. The addition of the compatibilizer to TLCP/LDPE blends significantly increased the melt viscosity due to increased interfacial adhesion. The TLCP/EAA‐Na ratio used to prepare the compatibilizer had little effect on the performance of the compatibilizer. Although the compatibilizer can be prepared in situ by blending and extruding a ternary blend of TLCP/EAA‐Na/polyethylene, pre‐reacting the compatibilizer resulted in blends with improved toughness and elongation.     

聚丙烯接枝衣康酸增容PA6／PP共混物性能及形态研究

采用反应型双螺杆挤出机和熔融接枝技术制备了一系列聚丙烯（PP）接枝物，包括单一单体接枝物PP接枝衣康酸（PP-g-ITA）和双单体接枝物PP接枝ITA和苯乙烯[PP-g-（ITA-co-St）]，通过红外光谱和热分析研究了PP接枝物的结构，并研究了PP接枝物的接枝率和熔体流动速率与单体和引发剂用量的关系。通过反应挤出制备了PP接枝物增容PA6／PP共混物，研究了增容共混物的力学性能和形态结构。结果显示：加入接枝物后，共混体系的冲击强度明显提高；SEM观察表明，接枝物的加入能明显改善增容共混物的两相界面结合状况，降低共混物的分散相尺寸，改善体系的分散状况，共混物的两相界面变得模糊，相容性得到明显提高；DSC测试表明，加入接枝物后，共混物中PA6组分的结晶度下降，PP组合的结晶度上升。表明PP-g-ITA是PA6／PP共混体系有效的增容剂兼增韧剂。     

PA6含量对PVC/PA6共混物形态结构与力学性能的影响

以EVA-g-MAH为相容剂,将PVC与自制的低熔点PA6共混制备了PVC/PA6共混物。通过扫描电子显微镜(SEM)和力学性能测试研究了PA6含量对PVC/PA6共混物形态结构及力学性能的影响。SEM分析结果显示:随着PA6含量的增加,PVC/PA6共混物的分散相尺寸逐渐增大,当PA6含量为10%时,共混物中分散相的分散尺寸最小为1μm;当PA6含量为50%时,共混物为两相共连续结构;当PA6含量为60%时,共混物中PA6为连续相,PVC为分散相。力学性能测试结果表明:当PA6含量为10%时,共混物的缺口冲击强度和拉伸强度都较PVC有明显提高,分别提高了约50%与30%,达到了6.29kJ/m2和60MPa。采用差示扫描量热仪(DSC)研究了PVC/PA6共混物的结晶温度,检测结果显示:PVC/PA6共混物呈现非晶结构。     

Phase morphology,thermomechanical, and crystallization behavior of uncompatibilized and PP‐g‐MAH compatibilized polypropylene/polystyrene blends

In this article, we discuss the phase morphology, thermal, mechanical, and crystallization properties of uncompatibilized and compatibilized polypropylene/polystyrene (PP/PS) blends. It is observed that the Young's modulus increases, but other mechanical properties such as tensile strength, flexural strength, elongation at break, and impact strength decrease by blending PS to PP. The tensile strength and Young's modulus of PP/PS blends were compared with various theoretical models. The thermal stability, melting, and crystallization temperatures and percentage crystallinity of semicrystalline PP in the blends were marginally decreased by the addition of amorphous PS. The presence of maleic anhydride‐grafted polypropylene (compatibilizer) increases the phase stability of 90/10 and 80/20 blends by preventing the coalescence. Hence, finer and more uniform droplets of PS dispersed phases are observed. The compatibilizer induced some improvement in impact strength for the blends with PP matrix phase, however fluctuations in modulus, strength and ductility were observed with respect to the uncompatibilized blend. The thermal stability was not much affected by the addition of the compatibilizer for the PP rich blends but shows some decrease in the thermal stability of the blends, where PS forms the matrix. On the other hand, the % crystallinity was increased by the addition of compatibilizer, irrespective of the blend concentration. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42100.     

The effects of SEBS-g-maleic anhydride reaction on the morphology and properties of polypropylene/PA6/SEBS ternary blends

Ternary blends, based on 70% by weight of polypropylene (PP) with 30% by weight of a dispersed phase, consisting of 15% polyamide-6 (PA6) and 15% of a mixture comprising varying ratios of an unreactive poly[styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS) triblock copolymer and a reactive maleic anhydride-grafted SEBS-g-MA, were produced via melt blending in a co-rotating twin-screw extruder. TEM revealed the blend containing only non-reactive SEBS to exhibit individual PA6 and SEBS dispersed phases. However, the progressive replacement of SEBS with reactive SEBS-g-MA increased the degree of interfacial reaction between the SEBS and PA6 phases, thus reducing interfacial tension and providing a driving force for encapsulation of the PA6 by the SEBS. Consequently, the dispersed-phase morphology was observed to transform from two separate phases to acorn-type composite particles, then to individual core-shell particles and finally to agglomerates of the core-shell particles. The resultant blends exhibited significant morphology-induced variations in both thermal and mechanical properties. DSC showed that blends in which the diameter of the PA6 particles was reduced to ≤3 μm by the increasing interfacial reaction exhibited fractionated PA6 crystallisation. In general, mechanical testing showed the blends to exhibit inferior low-strain tensile properties (modulus and yield stress) compared to the matrix PP, but superior ultimate tensile properties (stress and strain at break) and impact strength. These changes are discussed with reference to composite models.     

Compatibilization of PP/PE blends and scraps with Royalene: Mechanical properties,SAXS, and WAXS

PP/PE 93/7 model virgin blends and recycled scraps were compatibilized with Royalene (EPDM/PE 65/35 blend) and mechanically tested. No differences in impact and tensile properties between them were found. However, the tensile-impact strength increased almost twice with 10%-compatibilized sample in comparison with uncompatibilized ones. The yield stress of blends containing 10% Royalene decreased to 75–80% of the original value. This effect is in agreement with microhardness measurements; the increase in the compatibilizer content causes softening of the blend. The elongation at break and elongation at yield do not depend on the compatibilizer concentration. The compatibilizer does not influence the degree of crystallinity (WAXS data) of the blends either. Vickers microhardness is in good agreement with Tabor's relationship. The differences between long periods of HDPE in Royalene and LDPE in PP/PE blends (SAXS) proved PE/EPDM interaction. The interaction plays a key role in the toughening of PP/PE blends. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Studies on fracture behavior of tough PA6/PP blends

Fracture toughness of injection-molded PA6/PP blends compatibilized with SEBS-g-MA was studied using deeply double-edge notched tension (DDENT) specimens according to the essential work of fracture procedure. The fracture mechanical studies also included tensile impact tests on the DDENT specimens and characterization of the fracture surfaces by electron microscopy. The results were compared with those of traditional tensile tests and Izod impact tests on single-edge notched samples, and the sensibility of the methods was evaluated. Effects of sample position, ligament length, testing direction, and test speed were studied as well. It was found that the essential work of fracture concept, earlier applied to thin sheets, can also be applied to injection-molded tough blends. High deformation of the skin may, however, interfere with the measurements and cause a “tail” in the load-deformation curves. The plastic work of fracture (w_p) was found to correlate with the impact strength, and thus, it described the toughness. The highest values for work of fracture were recorded for the compatibilized blend with a PA6/PP ratio of 80/20. The essential work of fracture (w_e) in turn increased with increasing PA6 content and behaved like tensile strength. The test speed was found to affect the fracture behavior substantially: differences between the materials were more pronounced in high-speed tensile impact tests, which revealed signs of cavitation in addition to large-scale plastic deformation for the tough PA6-rich blend compositions. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2209–2220, 1997     

Compatibilization of PP/PBT and PP/PA6 blends with a new oxazoline-functionalized polypropylene

Summary Aim of this work was to study the effectiveness of a novel oxazoline-functionalized polypropylene as a compatibilizer for PP/PBT and PP/PA6 blends. This polypropylene-based compatibilizer mixes well with the polypropylene and is capable of reacting with the carboxylic and amine end groups of PBT and PA6. Significant improvements in blend toughness were achieved without reduction in strength and stiffness. These effects were related to stabilized morphology of finely dispersed minor phase well attached to the matrix. The enhanced interfacial interactions between the two phases, in particular at high PBT content were evidenced by increased melt viscosity.