有机蒙脱土对PA6/PP合金体系的作用机制及其对材料性能的影响

研究了有机蒙脱土对PA6/PP合金体系的作用机制及其对材料性能的影响。结果表明,OMMT的添加可以提高体系的拉伸强度、弯曲强度和弯曲模量,但冲击强度会有某种程度的下降;OMMT主要分散在PA6连续相中,且当其添加量质量份数低于5%时,可以在PA6相中实现较充分的剥离;OMMT对PA6/PP合金体系有着显著的增容作用,这可能和片层对PP分散相凝聚时的阻隔,以及片层所起到的类似接枝物的增容作用有关;OMMT在PA6基体中被充分剥离后,将有利于使复合体系的拉伸强度、弯曲强度得到提高,但OMMT片层及和片层有关的类似接枝物的存在,将束缚并限制界面层附近PP相的屈服,而使材料冲击韧性下降。     

Effect of ionomer on clay dispersions in polypropylene‐layered silicate nanocomposites

In this study, polypropylene (PP)/clay nanocomposites containing different concentrations of ethylene‐methacrylic acid ionomer (i.e. Surlyn®) were prepared, and the effect of ionomer on clay dispersion was studied via WAXD, rheology, SEM, and TEM. The role of the ionomer in the nanocomposites was compared with that of maleic anhydride grafted PP (PP‐g‐MA), which has been widely used as a compatibilizer in making PP/clay nanocomposites. With an increase in the concentration of compatibilizer, the position of d₀₀₁ peak of OMMT shifted toward a lower angle for PP‐g‐MA system, while the position remained almost unchanged for Surlyn system, in which a larger interlayer spacing (d₀₀₁) was found with respect to the former. In rheology, the addition of the ionomer led to a gradual increase in both moduli and complex viscosity, and the nonterminal behavior at low frequency was observed in both systems. In addition, the ternary hybrid containing 20 wt % Surlyn achieved the largest enhancement in relative viscosity, which was more than that of the nanocomposite prepared from pure Surlyn or pure PP, presumably indicative of the existence of strong interaction between the components. Finally, SEM and TEM micrographs demonstrated that exfoliated structure was preferred for PP/Surlyn/OMMT hybrids, while intercalated morphology for PP/PP‐g‐MA/OMMT. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4024–4034, 2007     

Solid‐state mechanical properties of polypropylene/nylon 6/clay nanocomposites

The mechanical and thermomechanical properties as well as microstructures of polypropylene/nylon 6/clay nanocomposites prepared by varying the loading of PP‐MA compatibilizer and organoclay (OMMT) were investigated. The compatibilizer PP‐MA was used to improve the adhesion between the phases of polymers and the dispersion of OMMT in polymer matrix. Improvement of interfacial adhesion between the PP and PA6 phases occurred after the addition of PP‐MA as confirmed by SEM micrographs. Moreover, as shown by the DSC thermograms and XRD results, the degree of crystallinity of PA6 decreased in the presence of PP‐MA. The presence of OMMT increased the tensile modulus as a function of OMMT loading due to the good dispersion of OMMT in the matrix. The insertion of polymer chains between clay platelets was verified by both XRD and TEM techniques. The viscosity of the nanocomposites decreased as PP‐MA loading increased due to the change in sizes of PA6 dispersed phase, and the viscosity increased as OMMT loading increased due to the interaction between the clay platelets and polymer chains. The clay platelets were located at the interface between PP and PA6 as confirmed by both SEM and TEM. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

成核剂对PET/PEN共混物性能影响及其机理研究

利用差示扫描量热法、X射线衍射和转矩流变测试等手段,研究了成核剂碳酸氢钠、苯甲酸钠和乙烯-甲基丙烯酸离子键聚合物(Surlyn)对聚对苯二甲酸乙二醇酯/聚萘二甲酸乙二醇酯（PET/PEN）共混物结晶性能和力学性能的影响。结果表明,3种成核剂均能显著提高共混物的成核作用,其中,Surlyn和苯甲酸钠能明显提高共混物结晶性能,结晶峰温度提高约20 ℃,结晶速度提升近1倍;3种成核剂中,只有Surlyn在提高结晶性能的同时,还能提高共混物的力学性能;Surlyn是PET/PEN共混物理想的成核剂。     

Thermal,mechanical, and barrier properties of polyethylene/surlyn/organoclay nanocomposites blown films prepared by different mixing methods

(Low‐density polyethylene) (LDPE)/clay nanocomposites were prepared by melt blending in a twin‐screw extruder by using different mixing methods. Zinc‐neutralized carboxylate ionomer was used as a compatibilizer. Blown films of the nanocomposites were then prepared. The effect of mixing method on the clay dispersion and properties of the nanocomposites was evaluated by wide‐angle X‐ray diffraction analysis, mechanical properties, thermal properties, and barrier properties. The structure and properties of nanocomposites containing different amounts of nanoclay prepared by selected mixing techniques were also investigated. It was found that melt compounding of Surlyn/clay masterbatch with pure LDPE and Surlyn (two‐step‐a method) results in better dispersion and intercalation of the nanofillers than melt mixing of LDPE/Surlyn/clay masterbatch with pure LDPE and surlyn (two‐step‐b method) and direct mixing of LDPE with clay. The films containing ionomer have good barrier properties. A wide‐angle X‐ray diffraction pattern indicates that intercalation of polymer chains into the clay galleries decreases by increasing the clay content. Barrier properties and tensile modulus of the films were improved by increasing the clay content. In addition, tensile strength increased in the machine direction, but it decreased in the transverse direction by increasing the clay content. DSC results showed that increasing the clay content does not show significant change in the melting and crystallization temperatures. The results of thermogravimetric analysis showed that the thermal stability of the nanocomposites decreased by increasing the clay content more than 1 wt%. J. VINYL ADDIT. TECHNOL., 21:60–69, 2015. © 2014 Society of Plastics Engineers     

Electrical and mechanical properties of partially bio-based PP/PBS blends nanocomposites elaborated by twin-screw extrusion

Organically modified montmorillonite (OMMT, Cloisite 20) was used as reinforcing filler to prepare nanocomposites from a blend of polypropylene (PP) and eco-friendly degradable polybutylene succinate (PBS). A PP grafted with maleic anhydride was also added as a compatibilizer. Scanning electron microscopy observations indicated that the blend morphology was affected by the presence of OMMT, which acted as a compatibilizer between PP and PBS. Rheological measurements showed a significant increase of the complex viscosity when OMMT was added above a certain amount. X-ray diffraction indicated an intercalated structure for all nanocomposites. The addition of OMMT improved mechanical properties of neat matrices and blends. The electrical insulation properties were preserved for low concentrations of OMMT, up to 2 wt%. Then, to guarantee good mechanical properties without deteriorating electrical ones, while maintaining a sufficient bio-based composition, the 70/30 (PP/PBS) blend with clay concentrations of less than 2 wt% appeared to be the most satisfactory nanocomposite for applications in the field of electrical insulation.     

The compatibilizing effect of poly(styrene-co-4-vinylpyridine) copolymers on the polystyrene–polyethylene-based ionomer blends

The compatibilizing effect of styrene-co-4-vinylpyridine (SVP) random copolymers on the immiscible polystyrene (PS)–polyethylene-based ionomer (Surlyn) blends was examined by means of scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, and tensile test. For the binary SVP–Surlyn and ternary PS–Surlyn–SVP blends, the domain size of dispersed phase decreases dramatically with the increase in the vinyl pyridine (VP) content of the SVP copolymers. The mechanical properties are improved with increasing the VP content in copolymers. FTIR results suggest that the compatibilization in this blend system is attributed to the ion–dipole interaction between the polar VP groups of SVP copolymer and ionic groups of Surlyn. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 807–816, 1998     

Rheological properties,tensile properties,and morphology of PP/EPDM/lonomer ternary blends

The rheological and tensile properties and the morphology of polypropylene (PP)/ethylenepropylene-diene terpolymer(EPDM)/ionomer ternary blends were investigated, using a rheometric dynamic spectrometer (RDS), a dynamic mechanical thermal analyzer (DMTA), a tensile tester, and a scanning electron microscope (SEM). Two kinds of poly(ethylene-co-methacrylic acid) (EMA) ionomers, neutralized with different metal ions (Na⁺ and Zn⁺⁺), were used. Blends were melt-mixed, using a laboratory internal mixer at 190°C. The composition of PP and EPDM was fixed at 50/50 by wt % and the EMA ionomer contents were varied from 5 to 20 wt %, based on the total amount of PP and EPDM. It was found that the ternary blends, containing Na-neutralized ionomer, showed considerably different rheological properties and morphology as compared to the PP/EPDM binary blends, due to the compatibilizing effect of the ionomer for PP and EPDM, while the ternary blends, containing the Zn-neutralized ionomer, did not. The compatibilizing effect was most prominent at 5 wt % ionomer concentration. © 1994 John Wiley & Sons, Inc.     

Effect of organoclay on the morphology, phase stability and mechanical properties of polypropylene/polystyrene blends

The effect of organically modified clay on the morphology, phase stability and mechanical properties of polypropylene (PP) and polystyrene (PS) blends was studied using three molecular weight grades of PP. Maleated polypropylene was used, at a PP-g-MA/organoclay ratio of 1, to preferentially promote dispersion of the organoclay in the PP matrix. The MMT content was fixed at 3 wt% based on the PP/PP-g-MA/MMT phase and the PS content was varied from 0-100 wt% in the blend. All blends were processed using a twin screw extruder. The organoclay resides in the PP phase and at the PP/PS interface. The dispersed PS particle size is significantly reduced by the presence of MMT, with maximum decrease observed for the low viscosity PP compared to its blend without MMT. The blends with MMT did not show any change in onset of co-continuity, though MMT shifts the phase inversion composition toward lower PS contents. The phase stability of the blend was significantly improved by the presence of MMT; for blends annealed at 210 °C for 2 h the dispersed phase particle size increased by as much as 10x without MMT with little change was noted with MMT present in the blend. The tensile modulus of blends improved with the addition of MMT at low PS contents. Blends based on the highest molecular weight grade PP showed increase in the tensile yield stress up to 40 wt% PS in the absence of MMT. The tensile strength at break for blend increased slightly with MMT while elongation at break and impact strength decreased in the presence of MMT. Surface energy analysis model was used to predict the orientation and equilibrium position of the clay platelet at the interface based on the surface energies.     

离聚物Surlyn对PTT/PA6共混物相容性的影响

通过扫描电镜(SEM)、差示扫描量热法(DSC)、傅立叶红外光谱(FTIR)研究了离聚物Surlyn对PTT/PA6共混物的相容性及形态结构的影响。PTT和PA6共混体系为热力学不相容体系,在共混物中加入一种离聚物聚甲基乙基丙烯酸锌(Surlyn),以提高共混物的相容性。实验结果表明,在以PTT为主体的PET/PA6简单共混物中,两者的相容性很差。加入离聚体Surlyn后,增加了界面粘接力,使分散相PA6的尺寸减小、分布趋向均匀。随着Surlyn的加入,PTT/PA/Surlyn共混体系的相容性得到了一定的提高。     

PP/黏土纳米复合材料的结构与性能

采用熔体插层法制备聚丙烯（PP）/有机黏土（OMMT）纳米复合材料。XRD和TEM的测试结果表明,采用熔体插层法制备的PP/OMMT复合材料是剥离型纳米复合材料。力学性能实验结果表明,相容剂的加入提高了PP与OMMT之间的相互作用,使其各项力学性能都得到了提高;PP/OMMT纳米复合材料的各项力学性能在有机黏土含量较小的情况下,就可以有较大幅度的提高;与纯PP相比,相容剂含量为10 phr、有机黏土用量为1 phr的聚丙烯基纳米复合材料具有最好的各项力学性能。     

The control of miscibility of PP/EPDM blends by adding lonomers and applying dynamic vulcanization

The control of miscibility for isotactic polypropylene (PP) and ethylene-propylene-diene terpolymer (EPDM) has been attempted by adding poly(ethylene-comethacrylic acid) (EMA) ionomers and by applying dynamic vulcanization. The rheological properties, crystallization behavior, and morphology of the dynamically vulcanized EPDM/PP/ionomer ternary blends were investigated with a Rheometrics dynamic spectrometer (RDS), a differential scanning calorimeter (DSC), and a scanning electron microscope (SEM). Two kinds of EMA ionomers neutralized with different metal ions (Na⁺ and ZN⁺⁺) were investigated. Blends were prepared on a laboratory internal mixer at 190°C. Blending and curing were performed simultaneously, i.e., EPDM was vulcanized with dicumyl peroxide (DCP) in the presence of PP/ionomer. The composition of PP and EPDM was fixed at 50/50 by wt% and the contents of EMA ionomer were vaired from 5 to 20 parts based on the total amount of PP and EPDM. It was found that the addition of ionomers and the application of the dynamic vulcanization were effective in enhancing the miscibility of PP and EPDM. The structure of the blends was controlled by the following three component phases, i.e., the phase of the dynamially valcanized EPDM, PP, and Zn-neutralized ionomer. The ternary blends showed more miscibility than the PP/EPDM binary blend. This is due to the thermoplastic interpenetrating polymer network (IPN) of the ternary blends. The structure and properties of the ternary blends differed, depending on the types and contents of ionomer, i.e., the ternary blend containing Na-neutralized ionomer did not show a thermoplastic IPN structure clearly, even though the blend was prepared by dynamic vulcanization. The ternary blend containing Zn-neutralized ionomer clearly showed the behavior of a thermoplastic IPN when the contents of ionomer and DCP were 15 parts and 1.0 part, respectively.     

顺丁烯二酸钾基(苯乙烯-丁二烯-苯乙烯)嵌段共聚物离聚体的力学性能及其应用

用环氧化(苯乙烯-丁二烯-苯乙烯)嵌段共聚物(SBS)开环反应合成了含顺丁烯二酸钾基的SBS离聚体,考察了离子基团不同含量对含顺丁烯二酸钾基的SBS离聚体力学性能的影响,研究了离聚体/聚丙烯(PP)共混物的力学性能和耐溶剂性能,以及离聚体对氯醇橡胶(CHR)/SBS共混物的增容效果。结果表明,该离聚体呈现热塑性弹性体行为;随着离子基团含量的增加,离聚体的拉伸强度及扯断伸长率增大,但当离子基团含量超过1.69mmol/g时,离聚体的力学性能又有所下降,离子基团最佳含量为1.23~1.69mmol/g;该离聚体与PP共混,在拉伸强度方面呈现协同效应;离聚体作为增容剂提高了SBS与CHR的相容性,当离聚体质量分数为3%时,力学性能达到最佳,共混物的耐溶剂性能也得到了改善。     

Use of a sodium ionomer as a compatibilizer in polypropylene/high‐barrier ethylene–vinyl alcohol copolymer blends: The processability of the blends and their physical properties

The effect of a sodium ionomer (ion.Na⁺) on the compatibility of polypropylene (PP)/high‐barrier ethylene–vinyl alcohol copolymer (EVOH) blends was studied in terms of the thermal, mechanical, and optical properties and morphology. The rheological behavior, tensile tests, and morphology of the binary blends showed that the miscibility of EVOH with PP was very poor. The miscibility of the polymers improved with the ionomer addition. In general, the ion.Na⁺ concentration did not alter the thermal behavior of the blends, but it did improve the ductility of the injection‐molded specimens. Scanning electron micrographs displayed better adhesion between the PP and EVOH phases in the samples with the ionomer. The mechanical improvement was better in the film samples than in the injection‐molded samples. A 90/10 (w/w) PP/EVOH film with 5% ion.Na⁺ and an 80/20 (w/w) PP/EVOH film with 10% ion.Na⁺ presented better global properties than the other blends studied. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1763–1770, 2004     

Ionomer compatibilised PA6/EVA blends: mechanical properties and morphological characterisation

The compatibilisation of PA6/EVA blends with the addition of an ionomer on the mechanical properties and morphology were studied as a function of ionomer concentration with the primary aim of enhancing the impact strength of PA6 by EVA. The level of EVA was kept at 20%, which formed the dispersed phase, and the ionomer content was varied from 0 to 1.6 wt%. It was found that notched Izod impact strength of PA6/EVA/ionomer blends increased with the incorporation of ionomer to about three times of the value for uncompatibilised PA6/EVA blends. Further, it was observed that on incorporation of the ionomer the tensile strength also increased significantly. Analysis of the tensile data using predictive theories indicated an enhanced interaction of the dispersed phase and the matrix. SEM studies of cryogenically fractured surfaces indicated a decrease in dispersed phase domain size with the addition of the ionomer, while the impact fractured surfaces of PA6/EVA blends indicated extensive deformation with the formation of rumples indicating increased interfacial adhesion as compared to PA6/EVA blends. An attempt has been made to evaluate the compatibilising efficiency of ionomer in PA6/EVA blends.     

The effect of compatibilizers and organically modified nanoclay on the morphology and performance properties of poly(acrylonitrile–butadiene–styrene)/polypropylene blends

In this study, poly(acrylonitrile–butadiene–styrene)/polypropylene (ABS/PP) blends with various compositions were prepared by melt intercalation in a twin‐screw extruder. Modifications of the above blends were performed by using organically modified montmorillonite (OMMT, Cloisite 30B) reinforcement as well as two types of compatibilizers, namely polypropylene grafted with maleic anhydride (PP‐g‐MAH) and ABS grafted with maleic anhydride (ABS‐g‐MAH). Increasing the PP content in ABS matrix seems to increase the melt flow and thermal stability of their blends, whereas a deterioration of the tensile properties was recorded. On the other hand, the addition of ABS to PP promotes the formation of the β‐crystalline phase, which became maximum at 30 wt% ABS concentration, and increases the crystallization temperature (T_c) of PP. A tendency for increase of T_c was also recorded by incorporation of the above compatibilizers, whereas the glass transition temperature (T_g) of PP and SAN phase in ABS was reduced. Regarding the Young's modulus, the greatest improvement was observed in pure ABS/PP blends containing organically modified nanoclay. However, in reinforced pure PP, the use of compatibilizers is recommended in order to improve the elastic modulus. The addition of OMMT to noncompatibilized and compatibilized ABS/PP blends significantly improves their storage modulus. POLYM. ENG. SCI., 56:458–468, 2016. © 2016 Society of Plastics Engineers     

Influence of the ethylene–(methacrylic acid)–Zn2+ ionomer on the thermal and mechanical properties of blends of poly(propylene) (PP)/ethylene–(vinyl alcohol) copolymer (EVOH)

The thermal and mechanical properties and the morphologies of blends of poly(propylene) (PP) and an ethylene–(vinyl alcohol) copolymer (EVOH) and of blends of PP/EVOH/ethylene–(methacrylic acid)–Zn²⁺ ionomer were studied to establish the influence of the ionomer addition on the compatibilization of PP/EVOH blends and on their properties. The oxygen transmission rate (O₂TR) values of the blends were measured as well. PP and EVOH are initially incompatible as was determined by tensile tests and scanning electronic microscopy. Addition of the ionomer Zn²⁺ led to good compatibility and mechanical behaviour was improved in all blends. The mechanical properties on extruded films were studied for 90/10 and 80/20 w/w PP/EVOH blends compatibilized with 10 % of ionomer Zn²⁺. These experiments have shown that the tensile properties are better than in the injection‐moulded samples. The stretching during the extrusion improved the compatibility of the blends, diminishing the size of EVOH domains and enhancing their distribution in the PP matrix. As was to be expected, the EVOH improved the oxygen permeation of the films, even in compatibilized blends. Copyright © 2004 Society of Chemical Industry     

Interfacially compatibilized LDPE/POE blends reinforced with nanoclay: investigation of morphology,rheology and dynamic mechanical properties

Morphological, melt rheological and dynamic mechanical properties of low-density polyethylene (LDPE)/ethylene–octene copolymer (POE)/organo-montmorillonite (OMMT) nanocomposites, prepared via melt compounding were studied. The XRD traces indicated different levels of intercalated structures for the nanocomposites. Addition of a compatibilizer (PE-g-MA) improved the intercalation process. TEM results revealed existence of clay layers in both phases but they were mainly localized in the elastomeric POE phase. Addition of 5 wt% OMMT to the LDPE/POE blend led to reduction in the size of the elastomer particles confirmed by AFM. The complex viscosity and storage modulus showed little effect of the presence of the clay when no compatibilizer was added. As the extent of exfoliation increased with addition of compatibilizer, the linear viscoelastic behavior of the composites gradually changed specially at low-frequency regions. The interfacially compatibilized nanocomposites with 5 wt% OMMT had the highest melt viscosity and modulus among all the studied nanocomposites and blends. Also, this particular composition showed the best improvement in dynamic storage modulus. The results indicated that clay dispersion and interfacial adhesion, and consequently different properties of LDPE/POE/clay nanocomposites, are greatly affected by addition of compatibilizer.     

界面增容剂的结构对PLA/PP共混体系界面状态及性能的影响

通过在聚乳酸(PLA)和聚丙烯(PP)共混体系中分别引入马来酸酐接枝乙烯-辛烯共聚物(POE-g-MAH)和甲基丙烯酸缩水甘油酯接枝乙烯-辛烯共聚物(POE-g-GMA),制备出具有不同结构及性能的共混材料(PLA/PP/POE-g-MAH,PLA/PP/POE-g-GMA),并采用转矩流变仪、扫描电子显微镜、差示扫描量热仪、平板流变仪及电子万能试验机等研究了不同界面增容剂的结构对PLA/PP共混体系界面状态及性能的影响。结果表明,POE-g-MAH和POE-g-GMA均可改善PLA与PP的相界面形态,但与POE-g-GMA相比,POE-g-MAH的界面催化效率更高,对PLA/PP共混体系增容效果更好,其可诱导PLA与PP在界面处形成微交联结构,增强PLA与PP的界面相互作用,改善材料的机械性能,当添加4wt%的POE-g-MAH时,PLA/PP/POE-g-MAH共混物的拉伸强度达29.7 MPa,断裂伸长率提升至39.3%,较PLA/PP样品提高了8倍;并且共混材料的冲击强度随着POE-g-MAH含量的增加而增加,当其添加量为6wt%时,材料冲击强度达30.1 kJ/m2,材料具有较好的刚韧平衡性。     

Interfacial modification of high density polyethylene/glass fiber reinforced and non reinforced polyamide 66 blends

High density polyethylene (HDPE) and polyamide (PA66) are well known to be incompatible. An ionomer (Surlyn) was added as a compatibilizer to HDPE and glass fiber reinforced (HDPE/GFRPA66) and non‐reinforced (HDPE/PA66) blends. Two compositions were considered: 25/75 wt % and 75/25 wt %, with an emphasis on the former formulation. The influence of the compatibilizer on the rheology, thermal properties, and the morphology, as well as mechanical properties of the blends, was investigated using melt flow index measurements, DSC, scanning electron microscopy (SEM), and impact strength. The ionomer was found to be more effective as a compatibilizer with HDPE as a minor phase compared to the case when HDPE becomes the major phase. The results indicated that the interfacial properties of the blends were improved, with a maximum appearing at a critical concentration of the ionomer (7.5 vol %). At this level of compatibilization, SEM analysis revealed better interfacial adhesion and a finer dispersion. MFI results revealed a probable reaction between the amine groups of PA66 and the acid functions of the ionomer. The mechanical properties support the above results and showed that the addition of 25 wt % HDPE did not affect the properties of PA66 much and the presence of glass fiber did not hinder the effect of the compatibilizer. Only 20% decrease in notched Izod impact strength of the blends is observed at 7.5 vol % ionomer content, suggesting that the addition of 25 wt % of HDPE to PA66 is not detrimental at this level of compatibilization. The emulsification curve was established and revealed that, in terms of impact properties, the finer the particle size, the higher the impact strength corresponding to 7.5 vol % ionomer content. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1748–1760, 2005