PP/EPDM/CaCO_3三元复合材料的相结构及力学性能研究

采用以化学键合方式在CaCO3表面包覆上聚丙烯蜡和将改性后的CaCO3先与EPDM复合、再与PP复合的工艺,制备PP/EPDM/CaCO3三元复合材料,以期在PP基体材料中得到EPDM包裹CaCO3的相结构.通过测量三元复合体系中各组分的表面张力,计算各可能组分对之间的界面张力和黏结功,分析三元复合体系中可能的相结构.热力学计算结果表明,三元复合体系中既存在以EPDM为壳、CaCO3为核的"核壳结构",又存在CaCO3与EPDM各自独立分散在PP基体中的结构.电镜照片进一步揭示,在PP/EPDM/改性CaCO3三元复合体系与PP/EPDM/未改性CaCO3三元复合体系中,这两种相结构的比例是不同的,在前者中以核壳结构为主.CaCO3表面性质的不同是产生这一差别的原因.由于这一结构差别的存在,PP/EPDM/改性CaCO3三元复合体系比PP/EPDM/未改性CaCO3三元复合体系具有更好的力学性能.当EPDM用量为8 phr、改性CaCO3用量为15 phr时,三元复合体系的冲击强度达14.25 kJ/m2,是纯PP的3.17倍.     

Effect of the interfacial interaction on the phase structure and rheological behavior of polypropylene/ethylene– octene copolymer/BaSO4 ternary composites

In polypropylene (PP)/ethylene–octene copolymer (POE)/BaSO₄ ternary composites, two different kinds of phase structures are assumed:(1) POE and BaSO₄ filler are separately dispersed in the PP matrix and (2) POE‐encapsulated filler particles (core–shell structure) are dispersed in the matrix. This depends on the interfacial interaction of the composites. For the design of composites with different interfacial interactions, three routes for the preparation of BaSO₄ master batches were developed. First, a mixture of BaSO₄, POE, and maleic anhydride (MAH) in a certain ratio was extruded in the presence of dicumyl peroxide and then pelletized. In extrusion, MAH‐functionalized POE was in situ formed to enhance the interfacial interaction between POE and BaSO₄. Second, a mixture of POE and BaSO₄ was directly extruded and then pelletized. Third, after BaSO₄ was treated with an organic titanate coupling agent, the treated BaSO₄ and POE were blended in extrusion and then pelletized. Scanning electron microscopy observations showed that the core–shell structure in which POE encapsulates BaSO₄ particles is formed through route 1, whereas POE and BaSO₄ are separately dispersed into the PP matrix through routes 2 and 3. The rheological behavior of PP/POE/BaSO₄ ternary composites was studied with a controlled stress rheometer. The results showed that the interfacial interaction in composites with core–shell morphology is the strongest. Interparticle interactions give rise to the formation of interparticle networks; the stronger the network is, the larger the shear yield stress is and the smaller the thixotropic loop area is. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1804–1812, 2002     

Blends of polycarbonate and ethylene-1-octylene copolymer

The mechanical properties and morphology of polycarbonate/ethylene-1-octylene copolymer (PC/POE) binary blends and PC/POE/ionomer ternary blends were investigated. The tensile strength and elongation at break of the PC/POE blends decreased with increasing the POE content. The impact strength of the PC/POE blends showed less dependence on thickness than that of PC. And the low-temperature impact strength of PC was modified effectively by addition of POE. The morphology of the PC/POE blends was observed by scanning electron microscope. The PC/POE weight ratio had a great effect on the morphology of the PC/POE blends. For the PC/POE (80/20)/ionomer ternary blends, low content (0.25 and 0.5 phr) of ionomer could increase the tensile properties of PC/POE (80/20) blend and had little effect on the impact strength. And 0.5 phr ionomer made the dispersed domain distribute more uniformly and finely than the blend without it. But with high content of ionomer, the degradation of PC made the mechanical properties of the blends deteriorate. Blending PC and ionomer proved the degradation of PC, and the molecular weight decreased with increasing the ionomer content.     

Preparation and properties of PP/PC/POE blends

In order to develop PP (polypropylene)‐based blends with balanced toughness and rigidity, the poly‐blends of PP/PC (polycarbonate)/POE (ethylene–octene copolymer) were prepared by applying styrene–ethylene–propylene–styrene (SEPS) as the macromolecular compatibilizer. The compatibilizing effect was studied in terms of the mechanical, morphologies and thermal properties, and the compatibilized PP‐based blends presented remarkable improvement in impact toughness and balanced tensile strength due to the formed special morphology structure. Additionally, by preparing the pre‐blend of PC/SEPS, the melt viscosity of the PP matrix can match that of the dispersed phase PC and POE, which led to a further improvement in the mechanical property of the blends. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of unsaturated hydroxyl-fatty acid modified nano-CaCO3 on the morphological and rheological behavior of PP

A modified nano-calcium carbonate (R-CCR) was prepared by coating a layer of unsaturated hydroxylfatty acid on the surface of CCR powders using a solid state method; the latter were commercial nano-CaCO₃ modified with stearic acid. FTIR studies indicate that the modifier is combined on the surface of CaCO₃. PP/EPDM/nano-CaCO₃ ternary composites were prepared by a melt-mixing method. SEM and TEM were utilized to examine the morphology of the composites. The tensile fractured surface of PP/EPDM/R-CCR showed a fibroid morphology and large-scale yield deformation. The impact fractured surface showed that the amount of cavities in the PP/EPDM/R-CCR system was increased, however their size diminished obviously. R-CCR particles were dispersed uniformly in the PP matrix, and their compatibility was distinctly improved as compared to CCR when the amount of R-CCR was 15 h⁻¹. The tensile strength remained nearly constant (reduced from 27.6 MPa to 27.5 MPa), while the impact strength increased from 9.6 kJ/m² to 15.4 kJ/m² as CCR was replaced by R-CCR. Meanwhile, the bending strength and bending modulus also increased correspondingly. Furthermore, the impact strength of PP/EPDM/R-CCR was maintained at a high level (15.4 kJ/m²), which was more than the sum of that of PP/EPDM and PP/R-CCR (6.6 kJ/m² and 6.1 kJ/m² respectively). This indicates that the R-CCR and EPDM have a significant synergistic toughening effect on PP while maintaining the strength and modulus of virgin PP. Both the storage modulus G′ and loss modulus G″ of PP/EPDM and PP/EPDM/R-CCR composites increase with increasing frequency, but the values of G′ and G″ of the tertiary composite are relatively higher than those of the binary system. The loss factor and viscosity decrease with increasing frequency, but there is little difference between tertiary and binary composites. The apparent viscosity η of the tertiary system containing R-CCR is lower than that of the tertiary system containing CCR and virgin PP. The viscosity of the composites sig-nificantly decreases with increasing shear rate. The mea-sured mechanical properties of the composites indicate that replacing CCR with R-CCR for binary composites could simultaneously enhance the toughness and strength of PP. __________ Translated from Acta Polymerica Sinica, 2008, 4 (in Chinese)     

羟基不饱和脂肪酸改性纳米碳酸钙对聚丙烯微观形态和流变性能的影响

采用羟基不饱和脂肪酸,通过固相法对硬脂酸改性的工业纳米碳酸钙CCR进行表面改性制备了R-CCR,红外光谱(FTIR)显示改性剂已结合在碳酸钙表面.通过熔融共混法制备了聚丙烯(PP)/乙丙橡胶(EPDM)/纳米碳酸钙二元和三元复合材料.并利用扫描电子显微镜(SEM)和透射电子显微镜(TEM)观察复合材料的微观形态,发现R-CCR的加入,使PP复合材料的拉伸断面出现明显的拉丝状结构和大面积的屈服变形,与PP/EPDM/CCR相比,PP/EPDM/R-CCR冲击断面的空穴明显增加并细化,R-CCR在PP基体中分散均匀,且界面模糊,与基体的相容性明显优于CCR.复合材料流变行为的研究表明R-CCR的加入,体系储存模量G′和损耗模量G″随频率的增加而增加,对损耗因子和复数粘度的影响不大;但PP/EPDM/R-CCR复合材料的表观粘度,明显低于PP/EPDM/CCR和纯PP,同时,剪切速率的增加可有效降低体系的表观粘度.力学性能表明,R-CCR对PP同时起到增韧和增强的效果.且R-CCR和EPDM对PP具有协同增韧的效果.在保持聚丙烯的模量和强度基本不变的前提下,大幅度的改善聚丙烯的韧性,同时加工性能保持不变.     

Ethylene–acrylic acid copolymer induced electrical conductivity improvements and dynamic rheological behavior changes of polypropylene/carbon black composites

The experimental data reveal that the addition of ethylene–acrylic acid copolymer (EAA) into carbon black (CB)/polypropylene (PP) composites can improve the electrical conductivity of CB/PP composites by two to six orders of magnitude at a comparatively low CB content (φ), and when φ = 2.5 vol %, 60/40 of PP/EAA is an optimum for electrical conductivity improvement. The dynamic rheological data show that with increasing φ there are apparent rheological percolations for CB/PP composites. A modified Kerner–Nielson equation can be used to describe the correlation between electrical percolation and dynamic viscoelastic percolation. The addition of EAA into CB/PP composites leads to apparent changes in dynamic rheological behaviors. When φ = 2.5 vol %, a rheological percolation appears in CB/PP/EAA (CPE) composites with increasing EAA content. The similar rheological behaviors correspond to the similar morphological structures for CPE composites with φ = 5.0 vol %. The appearance of bumps in the van‐Gurp–Palmen plots corresponds to the formation of network structure in CB/PP and CPE composites, and the more perfect the networks, the higher the amplitude of the bumps. All data indicate that the van‐Gurp–Palmen plot is sensitive to the formation of filler particle networks or cocontinuous phase which spans the whole composite. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1762–1771, 2009     

Highly toughened poly (acrylonitrile–styrene–acrylic)/chlorinated polyethylene blends: Mechanical,rheological and thermal properties

The effect of chlorinated polyethylene (CPE) on the properties of poly (acrylonitrile-styrene-acrylic) (ASA) was investigated. As an impact modifier, CPE effectively toughened ASA. With the addition of 15 phr CPE, the impact strength increased from 25.1 kJ/m² to 41.7 kJ/m². The morphology of the blends exhibited heterogeneous structure and correlated well with the results of impact strength. The glass transition temperature corresponding with ASA remained constant, indicating that CPE did not change the dual-phase structure of ASA. In rheological tests, the enhancement of storage modulus and complex viscosity of ASA, together with Cole-Cole plots, indicated that certain changes in phase structure existed after CPE content exceeded 8 phr. Thermogravimetric analysis results suggested that CPE slightly decreased the onset degradation temperature. Our study showed that CPE, as an impact modifier, can effectively improve the toughness of ASA.     

Effects of polystyrene‐b‐poly(ethylene/propylene)‐b‐polystyrene compatibilizer on the recycled polypropylene and recycled high‐impact polystyrene blends

The recycled polypropylene/recycled high‐impact polystyrene (R‐PP/R‐HIPS) blends were melt extruded by twin‐screw extruder and produced by injection molding machine. The effects of polystyrene‐b‐poly(ethylene/propylene)‐b‐polystyrene copolymer (SEPS) used as compatibilizer on the mechanical properties, morphology, melt flow index, equilibrium torque, and glass transition temperature (T_g) of the blends were investigated. It was found that the notch impact strength and the elongation at break of the R‐PP/R‐HIPS blends with the addition of 10 wt% SEPS were 6.46 kJ/m² and 31.96%, which were significantly improved by 162.46% and 57.06%, respectively, than that of the uncompatibilized blends. Moreover, the addition of SEPS had a negligible effect on the tensile strength of the R‐PP/R‐HIPS blends. Additionally, the morphology of the blends demonstrated improved distribution and decreased size of the dispersed R‐HIPS phase with increasing the SEPS content. The increase of the melt flow index and the equilibrium torque indicated that the viscosity of the blends increased when the SEPS was incorporated into the R‐PP/R‐HIPS blends. The dynamic mechanical properties test showed that when the content of SEPS was 10 wt%, the difference of T_g decreased from 91.72°C to 81.51°C. The results obtained by differential scanning calorimetry were similar to those measured by dynamic mechanical properties, indicating an improved compatibility of the blends with the addition of SEPS.     

Tailoring of interface of polypropylene/polystyrene/carbon nanofibre composites by polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene

Mechanical and physical properties of polypropylene (PP)/polystyrene (PS) blend, PP/PS/polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (SEBS) ternary blend and their composites with carbon nanofibers (CNF) were investigated. Composites of ternary blend exhibited superior properties compared to those of binary blends. Mechanical performance of nanocomposites was intimately related to their phase morphology. PP/PS/SEBS/0.1 wt% CNF hybrid composites exhibited excellent impact strength (Four-fold increase compared to PP/PS blend) and ductility (12-fold increase in elongation at break, with respect to PP/PS blend). Moreover, these composites displayed good tensile strength and modulus (15% increase in Young's modulus, compared to PP/PS/SEBS blend) and are suitable for various end-use applications including automobile applications. Although crystallinity of PP phase is decreased by the incorporation of CNF, thermal stability of the composites remained almost unaffected. Contact angle measurements revealed that ternary composites exhibited maximum hydrophobicity.     

Morphology and properties of polypropylene/ethylene–octene copolymer/clay nanocomposites with double compatibilizers

The influence of nanoclay on the morphology and properties of the polypropylene (PP)/ethylene–octene block copolymer (EOC) blend with double compatibilizers of maleated PP (PP‐g‐MA) and maleated EOC (EOC‐g‐MA) was investigated and compared with the nanocomposites containing either PP‐g‐MA or EOC‐g‐MA as a compatibilizer. X‐ray diffraction, transmission electron microscopy, and scanning electron microscopy were utilized for morphological characterization in conjunction with dynamic mechanical thermal analysis, mechanical testing, and rheological evaluation of these nanocomposites. The results suggested that in the nanocomposite including both compatibilizers of PP‐g‐MA and EOC‐g‐MA, clay was dispersed as a mixed structure of intercalation and exfoliation in both phases of the polymer blend. Comparing the mechanical properties of the studied nanocomposite with nanocomposites of PP/EOC/PP‐g‐MA/clay and PP/EOC/EOC‐g‐MA/clay also indicated that the nanocomposite containing mixed compatibilizers displayed higher tensile modulus, tensile strength, and complex viscosity because of the better dispersion of clay in both phases. The results also confirmed the increased structural stability and reduced dispersed phase size of PP/EOC/PP‐g‐MA/EOC‐g‐MA blend in the presence of clay that proposed the compatibilization role of clay in this nanocomposite. Copyright © 2014 John Wiley & Sons, Ltd.     

Simulation of mechanical properties of multilayered propylene–ethylene copolymer/ethylene 1-octene copolymer composites by equivalent box model and its experimental verification

Multilayered propylene–ethylene copolymer (PPE)/ethylene 1-octene copolymer (POE) composites were prepared by a microlayered coextrusion system. Static and dynamic tensile results showed that yield strengths and storage moduli of the multilayered samples were distinctly larger than those of conventional blends. The equivalent box model (EBM) proposed by Kolarik was used to explain the effect of morphology on mechanical properties. Experimental and theoretical results indicated that the excellent mechanical properties of multilayered composites were ascribed to the phase continuity. The effects of interfacial layers in multilayered composites on mechanical properties were also discussed. The existence of interfaces between POE and PPE layers not only led to the invalidation of EBM for prediction of mechanical properties of multilayered composites with larger number of layers, but also induced a new absorbing peak in loss modulus-temperature spectrum because of the shearing friction between POE and PPE layers through interfaces.     

颗粒内受限聚合法制备PP/POE/PS合金

以等规聚丙烯/乙烯-辛烯共聚物(PP/POE)合金颗粒为扩散基体, 苯乙烯(St)为扩散单体, 利用颗粒内受限聚合法制备了PP/POE/PS三元合金. 结果表明, 对于POE质量分数为20%~40%的PP/POE合金颗粒, St均可扩散至直径为4 mm的颗粒中心部位, 在POE非晶相中生成相尺寸为几十至几百纳米的PS球. 在PP/POE合金颗粒的不同部位, 因POE相尺寸及单体的吸附量不同, 生成的PS相尺寸也不同, 在颗粒中心部位生成的PS球最小. 研究了St在PP/POE(质量比80: 20)颗粒中的扩散-聚合行为, 结果表明, St在合金颗粒中的扩散速率和扩散饱和值远大于在纯PP颗粒中的扩散速率和饱和值, 这主要是因为PP/POE合金颗粒中的非晶POE相有利于扩散. 改变单体投料量可以获得具有不同PS含量的PP/POE/PS三元合金. 结晶性能研究结果表明, PS在非晶POE相中的优先分布会使POE相体积增大, 从而使PP的结晶温度和熔融温度降低. 随着PS量的进一步增大, 分布在PP中的PS对PP有结晶成核作用.     

Structure and mechanical properties of SRP/HDPE/POE (EPR or EPDM) composites

The effects of dicumyl peroxide (DCP) and ethylene-octylene copolymer (POE), ethylene-propylene copolymer (EPR) or ethylene-propylene-diene terpolymer (EPDM) on the structure and properties of scrap rubber powder (SRP)/high-density polyethylene (HDPE) composites were studied. Torque and gel content results show that DCP promotes crosslinking of the SRP/HDPE/POE (EPR or EPDM) composites. The SRP/HDPE/POE (EPR or EPDM) composites containing a small amount of DCP have better mechanical properties than their corresponding composites without DCP. Highest tensile strength and elongation at break are found in the dynamically vulcanized SRP/HDPE/POE composite. Scanning electron microscopy (SEM) results show that good bonding between SRP and matrix is formed in the SRP/HDPE/POE (EPR or EPDM) composites with DCP.     

Simultaneous enhancement of electrical conductivity and impact strength via formation of carbon black‐filler network in PP/EPDM Blends

The electrical conductivity and impact strength of polypropylene(PP)/EPDM/carbon black ternary composites were investigated in this paper. Two processing methods were employed to prepare these ternary composites. One was called one‐step processing method, in which the elastomer and the filler directly melt blended with PP matrix. Another one was called two‐step processing method, in which the elastomer and the filler were mixed first, and then melt blended with pure PP. To get an optimal phase morphology that favors the electrical conductivity and impact strength, controlling the distribution of CB in PP/EPDM blend was a crucial factor. Thus the interfacial tension and the work of adhesion were first calculated based on the measurement of contact angle, and the results showed that CB tended to be accumulated around EPDM phases to form filler‐network structure. Expectably, the filler‐network structure was observed in PP/EPDM/CB(80/20/3) composite prepared by two‐step processing method. The formation of this filler‐network structure decreased the percolation threshold of CB particles in polymer matrix, and the electrical conductivity as well as Izod impact strength of the composite increased dramatically. This work provided a new way to prepare polymer composites with both improved conductivity and impact strength. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of gamma radiation on the performance of jute fabrics-reinforced polypropylene composites

Jute fabrics-reinforced polypropylene (PP) composites (50% fiber) were prepared by compression molding. Composites were fabricated with non-irradiated jute fabrics/non-irradiated PP (C-0), non-irradiated jute fabrics/irradiated PP (C-1), irradiated jute fabrics/non-irradiated PP (C-2) and irradiated jute fabrics/irradiated PP (C-3). It was found that C-3 composite performed the best mechanical properties over other composites. Total radiation dose varied from 250–1000 krad and composites made of using 500 krad showed the best results. The optimized values (C-3 composites) for tensile strength (TS), bending strength (BS) and impact strength (IS) were found to be 63 MPa, 73 MPa and 2.93 kJ/m², respectively.     

聚丙烯/纳米级金红石型二氧化钛/聚烯烃弹性体复合材料的抗老化性能研究

采用TEM和UV-Vis等测试手段表征了金红石型纳米级TiO2和体相TiO2的性能特征;通过熔融共混法分别制备了PP/纳米级TiO2/POE和PP/体相TiO2/POE复合材料,采用GB/T16422·2-1999所述的塑料实验室光源暴露实验方法,用氙灯气候试验机对纯PP和复合材料进行28天人工加速老化.结果表明,二氧化钛粒子在PP/POE基体中分散性良好,而纳米粒子对PP/POE基体具有增韧作用;改性后的两类复合材料均具有优异的抗老化性能,而PP/(1·0wt%)纳米级TiO2/POE复合材料的抗老化性能更加优异,其加速老化28天后的无缺口冲击强度达到80·45kJ·m-2,比纯PP提高4倍多,而同期加速老化28天后的PP/(1·0wt%)体相TiO2/POE复合材料的无缺口冲击强度只有47·88kJ·m-2;对纯PP老化过程中的羰基指数和冲击性能的变化情况进行了分析,发现二者近似成线性关系,其相关系数r在0·9以上.     

New (PP/EPR)/nano‐CaCO3 based formulations in the perspective of polymer recycling. Effect of nanoparticles properties and compatibilizers

Phase structure of composite polypropylene (PP)/ethylene–propylene–rubber (EPR)/coated nano‐CaCO₃ composites, used in the manufacture of bumpers, with and without compatibilizers has been investigated using scanning electron microscopy (SEM), dynamic mechanical analysis (DMA) mechanical tests, and differential scanning calorimetry (DSC). Blends of various compositions were prepared using a corotating twin‐screw extruder. The experimental results indicated that the dispersion of nanoparticles in (PP/EPR) depends on their surface (stearic acid and fatty acid coatings). In both cases, the final morphology is the core–shell structure in which EPR acts as the shell part encapsulating coated nano‐CaCO₃. In this case, EPR‐g‐MAH copolymer does not improve the interface between (PP/EPR) and nanoparticles but PEP propylene ethylene copolymer should be preferentially localized at the interface of PP and (EPR/nano‐CaCO₃) phases generating an improved adherence, which will ensure a better cohesion of the whole material. According to the nature of the compatibilizers and surface treatment, it is believed that the synergistic effect of both the EPR elastomer and CaCO₃ nanoparticles should account for the balanced performance of the ternary composites. Copyright © 2009 John Wiley & Sons, Ltd.     

纳米SiO_2/聚丙烯复合材料的反应性增容

利用反应性增容技术制备了纳米二氧化硅/聚丙烯复合材料.首先探讨了将甲基丙烯酸缩水甘油酯-丙烯酸丁酯共聚物接枝到纳米二氧化硅粒子表面进行改性的各种影响因素,然后将接枝改性纳米二氧化硅与聚丙烯以及作为反应性增容剂的氨基化聚丙烯共混.结果表明,改性粒子上的环氧基与氨基化聚丙烯上的氨基之间的化学反应大大增强了复合材料的界面作用,从而在粒子含量很低时明显提高了聚丙烯的拉伸强度、模量和冲击强度.     

Effect of nucleating agent on the brittle–ductile transition behavior of polypropylene/ethylene–octene copolymer blends

In the present work, α‐form nucleating agent 1,3:2,4‐bis (3,4‐dimethylbenzylidene) sorbitol (DMDBS, Millad 3988) is introduced into the blends of polypropylene/ethylene–octene copolymer (PP/POE) blends to study the effect of the nucleating agent on the toughness of PP/POE blends through affecting the crystallization behavior of PP matrix. Compared with the PP/POE blends, in which the toughness of the blends increases gradually with the increasing content of POE and only a weak transition in toughness is observed, addition of 0.2 wt % DMDBS induces not only the definitely brittle‐ductile transition at low POE content but also the enhancement of toughness and tensile strength of the blends simultaneously. Study on the morphologies of impact‐fractured surfaces suggests that the addition of a few amounts of DMDBS increases the degree of plastic deformation of sample during the fracture process. WAXD results suggest that POE induces the formation of the β‐form crystalline of PP; however, DMDBS prevents the formation of it. SEM results show that the addition of DMDBS does not affect the dispersion and phase morphologies of POE particles in PP matrix. DSC and POM results show that, although POE acts as a nucleating agent for PP crystallization and which enhances the crystallization temperature of PP and decreases the spherulites size of PP slightly, DMDBS induces the enhancement of the crystallization temperature of PP and the decrease of spherulites size of PP more greatly. It is concluded that the definitely brittle–ductile transition behavior during the impact process and the great improvement of toughness of the blends are attributed to the sharp decrease of PP spherulites size and their homogeneous distribution obtained by the addition of nucleating agent. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 577–588, 2008