Compatibilizers for recycling of the plastic mixture wastes. II. The effect of a compatibilizer for binary blends on the properties of ternary blends

In this article, we discuss the effect of a compatibilizer for binary blends on the properties of ternary blends composed of high‐density polyethylene (HDPE), polypropylene (PP), or polystyrene (PS) and poly(vinyl chloride) (PVC) virgin polymers with a simulated waste plastics fraction. Chlorinated polyethylene (CPE), ethylene–propylene rubber (EPR), and their 1/1 (w/w) mixture were tested as compatibilizers for the HDPE/PP/PVC ternary blend. CPE, styrene‐ethylene‐propylene block copolymer (SEP), or their 1/1 (w/w) mixture were tested as compatibilizers for the HDPE/PS/PVC ternary blend. The composition of the ternary blends were fixed at 8/1/1 by weight ratio. The amount of the compatibilizer was 3 phr. Rheological, mechanical, and thermal properties were measured. For the 8/1/1 HDPE/PP/PVC ternary blends, the tensile strength was slightly decreased, but the impact strength was significantly increased by adding EPR, CPE, or their mixture. EPR exhibited the most significant impact modification effect for the ternary blends. In a similar way, for 8/1/1 HDPE/PS/PVC ternary blends, on adding SEP, CPE, or their mixture, the tensile strength was slightly decreased, but the impact strength was noticeably increased. It was found that the SEP worked much better as an impact modifier for the ternary blends than CPE or the SEP/CPE mixture did. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1048–1053, 2000     

化学交联PE-LD/SBS共混物的形状记忆效应研究

分别用3种不同苯乙烯含量的苯乙烯-丁二烯共聚物(SBS)与低密度聚乙烯(PE-LD)混合制成共混物,采用过氧化苯甲酰(BPO)为引发剂,使共混物发生化学交联形成网状结构,对交联共混物的交联度进行了分析,测试了交联共混物的拉伸强度与断裂伸长率,探讨了交联共混物的形状记忆效应。结果表明,在PE-LD/SBS共混物中,随着BPO含量的增加,共混物的交联度增大;BPO含量固定时,随着SBS中丁二烯含量的增大共混物的交联度增大;随着交联度的增加,共混物的拉伸强度与断裂伸长率均下降;当BPO含量为0.5 %～1.5 %时,交联共混物具有良好的形状记忆效应。     

Phase dispersion–crosslinking synergism in binary blends of poly(vinyl chloride) with low‐density polyethylene: Entrapping phenomenon in PVC/LDPE/DCP blend

The co‐crosslinked products and the entrapping phenomenon that may exist in a poly(vinyl chloride)/low density polyethylene/dicumyl peroxide (PVC/LDPE/DCP) blend were investigated. The results of selective extraction show that unextracted PVC was due to not being co‐crosslinked with LDPE but being entrapped by the networks formed by the LDPE phase. SBR, as a solid‐phase dispersant, can promote the perfection of networks of the LDPE phase when it is added to the PVC/LDPE blends together with DCP, which leads to more PVC unextracted and improvement of the mechanical properties of PVC/LDPE blends. Meanwhile, the improvement of the tensile properties is dependent mainly on the properties of the LDPE networks. Finally, the mechanism of phase dispersion–crosslinking synergism is presented. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1296–1303, 2003     

Dynamic vulcanization of recycled milk pouches (LDPE–LLDPE) and EPDM blends using dicumyl peroxide

The viability of thermomechanical recycling of post‐consumer milk pouches (blend of low‐density polyethylene (LDPE) and linear low‐density polyethylene (LLDPE)) and its scope for suitable engineering applications were investigated. The effects of blending with ethylene‐propylene‐diene monomer (EPDM) rubber and subsequent curing using dicumyl peroxide (DCP) on the macromolecular structure and properties of recycled polyethylene (PE) blends were studied. The crosslinking efficiency of recycled PE/EPDM blends and possible thermooxidative degradation of recycled polymer upon peroxide curing was assessed using torque and gel content measurements along with infrared spectroscopic analysis. Both the torque and gel content of the blends varied with DCP crosslinking reactions and also were affected by oxidative degradation. In view of the electrical application area of this recycled blend material, the dielectric breakdown strength and volume resistivity were measured. The mechanical performance and thermal stability of recycled PE/EPDM blends improved with progressive crosslinking by DCP but deteriorated somewhat at higher DCP dose. Scanning electron microscopy showed good interface bonding between recycled polymer and dispersed EPDM phase in the cured blends compared to the non‐cured blends. Copyright © 2007 Society of Chemical Industry     

Mechanical property and morphology comparison between the two blends poly(propylene)/ethylene‐propylene‐diene monomer elastomer and poly(propylene)/maleic anhydride‐g‐ethylene‐propylene‐diene monomer

The comparison of the mechanical properties between poly(propylene)/ethylene‐propylene‐diene monomer elastomer (PP/EPDM) and poly(propylene)/maleic anhydride‐g‐ethylene‐propylene‐diene monomer [PP/MEPDM (MAH‐g‐EPDM)] showed that the latter blend has noticeably higher Izod impact strength but lower Young's modulus than the former one. Phase morphology of the two blends was examined by dynamic mechanical thermal analysis, indicating that the miscibility of PP/MEPDM was inferior to PP/EPDM. The poor miscibility of PP/MEPDM degrades the nucleation effectiveness of the elastomer on PP. The observations of the impact fracture mode of the two blends and the dispersion state of the elastomers, determined by scanning electron microscopy, showed that PP/EPDM fractured in a brittle mode, whereas PP/MEPDM in a ductile one, and that a finer dispersion of MEPDM was found in the blend PP/MEPDM. These observations indicate that the difference in the dispersion state of elastomer between PP/EPDM and PP/MEPDM results in different fracture modes, and thereby affects the toughness of the two blends. The finer dispersion of MEPDM in the blend of PP/MEPDM was attributed to the part cross‐linking of MEPDM resulting from the grafting reaction of EPDM with maleic anhydride (MAH) in the presence of dicumyl peroxide (DCP). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2486–2491, 2002     

Influences of dicumyl peroxide on morphology and mechanical properties of polypropylene/poly(styrene‐b‐butadiene‐b‐styrene) blends via vane‐extruder

Polypropylene (PP) and poly(styrene‐b‐butadiene‐b‐styrene) block copolymer (SBS) were melt‐blended in the presence of initiator system. Dicumyl peroxide (DCP)/Triallyl isocyanurate (TAIC) via self‐deigned VE, aiming at in situ reactive compatibilization of toughed PP/SBS blend. The reactivity, morphology and mechanical properties of PP/SBS/DCP/TAIC blends were studied. Online torque detection was conducted to monitor changes in viscosities of reactive compatibilized blends, which could give proof of the interfacial grafted reaction induced by DCP/TAIC system. The effect of reactive compatibilization on the dispersed particles sizes and interfacial adhesion was studied by scanning electron microscopy. Analysis on mechanical performance revealed the impact strength improved after treated by initiator system, moreover, the impact‐fractured surface observation showed, the failure mode changed from debonding mechanism of neat 50PP/50SBS blend to plastic deformation mechanism of blend containing 3.0 phr initiator system. With improved interfacial adhesion, compatibilized blends not only were toughened but also exhibited enhanced tensile strength and thermal stability. Dynamic mechanical analysis showed a reduction of between PP phase and the PB segments in SBS phase, indicating reactive compatibilization of the blend was achieved. In the final part, a brief discussion was given about the dominant effects from chain scission of PP matrix to intergrafting reactions of PP and SBS, under different content of DCP/TAIC initiator system. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41543.     

Rheological properties and crystalline structure of the dynamically cured EPDM and PP/HDPE ternary blends

The rheological properties and crystalline structure of the polyolefin ternary blends of EPDM/polypropylene/high density polyethylene were studied. Blends were prepared in a laboratory internal mixer by two different methods. In blend–cure process, blending and curing were performed simultaneously and EPDM was cured by dicumyl peroxide (DCP) in the presence of PP/HDPE under shear. The cure–blend was to cure EPDM alone first under shear (dynamic curing) and then mix the cured EPDM with PP and HDPE. The effect of DCP concentration, intensity of the shear mixing, and the rubber/plastic composition were studied using capillary rheometer and X-ray diffractometer. The PP-rich ternary blends showed the effect of the mechanooxidative degradation of PP by shear and peroxide. The melt viscosity increased with increasing DCP concentration in blends of EPDM-rich compositions. X-ray diffraction studies revealed that the inclusion of 25 wt % of linear EPDM in the PP/HDPE mixture for the PP-rich ternary blends changed the crystal structure of polypropylene component in the ternary blends. However, the dynamic curing did not alter the crystal structure of PP or HDPE in the blends.     

SBS and SEBS block copolymers as impact modifiers for polypropylene compounds

Blends of polypropylene (PP) and thermoplastic elastomers (TPE), namely SBS (styrene‐butadiene‐styrene) and SEBS (styrene‐ethylene/1‐butene‐styrene) block copolymers, were prepared to evaluate the effectiveness of the TPE type as an impact modifier for PP and influence of the concentration of elastomer on the polymer properties. Polypropylene homopolymer (PP‐H) and ethylene–propylene random copolymer (PP‐R) were evaluated as the PP matrix. Results showed that TPEs had a nucleating effect that caused the PP crystallization temperature to increase, with SBS being more effective than SEBS. Microstructure characterization tests showed that in most cases PP/SEBS blends showed the smallest rubber droplets regardless of the matrix used. It was seen that SEBS is a more effective toughening agent for PP than SBS. At 0°C the Izod impact strength of the PP‐H/SEBS 30% b/w blend was twofold higher than the SBS strength, with the PP‐R/SEBS 30% b/w blend showing no break. A similar behavior on tensile properties and flexural modulus were observed in both PP/TPE blends. Yield stress and tensile strength decreased and elongation at break increased by expanding the dispersed elastomeric phase in the PP matrix. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 254–263, 2005     

EPDM/聚烯烃共混型热塑性弹性体的研究

制备ＥＰＤＭ／聚烯烃简单共混型热塑性弹性体。研究了聚合物种类、橡塑比、二元和三元共混对共混物力学性能的影响。结果表明，部分结晶性ＥＰＤＭ共混物的力学性能比无定形ＥＰＤＭ共混物好，部分结晶性ＥＰＤＭ与ＬＤＰＥ（低密度聚乙烯）共混物的拉伸强度大于两者的加和值，而其它二元共混物的拉伸强度均低于两共混单元的加和值；用ＬＤＰＥ部分替代ＰＰ，或用氯磺化聚乙烯（ＣＳＭ）部分替代结晶性ＥＰＤＭ进行三元共混，能改善部分结晶性ＥＰＤＭ／ＰＰ共混物的某些性能。     

Tensile properties and morphology of the dynamically cured EPDM and PP/HDPE ternary blends

The tensile properties and morphology of the polyolefin ternary blends of ethylenepropylene–diene terpolymer (EPDM), polypropylene and high density polyethylene were studied. Blends were prepared in a laboratory internal mixer where EPDM was cured in the presence of PP and HDPE under shear with dicumyl peroxide (DCP). For comparison, blends were also prepared from EPDM which was dynamically cured alone and blended with PP and HDPE later (cure–blend). The effect of DCP concentration, intensity of the shear mixing, and rubber/plastics composition was studied. The tensile strength and modulus increased with increasing DCP concentration in the blends of EPDM-rich compositions but decreased with increasing DCP concentration in blends of PP-rich compositions. In the morphological analysis by scanning electron microscopy (SEM), the small amount of EPDM acted as a compatibilizer to HDPE and PP. It was also revealed that the dynamic curing process could reduce the domain size of the crosslinked EPDM phase. When the EPDM forms the matrix, the phase separation effect becomes dominant between the EPDM matrix and PP or HDPE domain due to the crosslinking in the matrix.     

Blends of i‐PP and SBS. II. Influence of in situ compatibilization on the mechanical properties

This article concerns the in situ compatibilization of immiscible isotatic polypropylene/styrene–butadiene–styrene triblock copolymer blends (i‐PP/SBS) by use of a reactive mixture. For this purpose, maleated PP (PP–MAH) and SBS (SBS–MAH) were used as functionalized polymers and 4,4′‐diaminediphenylmethane was used as a coupling agent between maleated polymers, resulting in a graft copolymer. Binary blends of i‐PP/SBS, nonreactive ternary blends of i‐PP/PP–MAH/SBS, and reactive ternary blends of i‐PP/PP–MAH/SBS–MAH with varying diamine/anhydride molar ratios were prepared. The mechanical properties of the blends were determined by tensile and impact‐resistance tests. The optimum improvement in the mechanical properties was found when the diamine/anhydride molar ratio in the ternary reactive blends was 0.5/1. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 516–522, 2003     

Interfacial adhesion evaluation in (low‐density polyethylene)/elastomer blends

Low‐density polyethylene (LDPE) with different elastomers at a ratio of 50/50 wt% blends was prepared by using a co‐rotating twin‐screw extruder. Three kinds of elastomers were used: ground tire rubber (GTR), partially crosslinked butyl rubber (Kalar^®), and styrene‐butadiene‐rubber block copolymer (SBS; Kraton^®). For better characterization of interaction between polyethylene and elastomer, influence of the type of elastomer on the properties of compositions LDPE/elastomer was determined. In the studies, two types of partially crosslinked butyl rubber (differing over filler content and Mooney viscosity) and two types of SBS (differing over structure: linear/branched) were used. The influence of kind and type of elastomer on static mechanical properties (tensile strength, elongation at break, hardness), dynamic mechanical properties, thermal properties, and morphology of obtained compositions were characterized. LDPE/linear SBS copolymer blend had the best mechanical properties, as a result of better compatibility in comparison with other investigated blends. The reason for improved compatibility was an increase of mobility of chain segments in the amorphous phase of polyethylene associated with their partial plasticization by flexible polybutadiene blocks present in SBS copolymer. J. VINYL ADDIT. TECHNOL., 22:492–500, 2016. © 2015 Society of Plastics Engineers     

Influence of phase modifiers on morphology and properties of thermoplastic elastomers prepared from ethylene propylene diene rubber and isotactic polypropylene

A series of thermoplastic elastomers (TPEs) were prepared from a binary blend of ethylene propylene diene rubber (EPDM) and isotactic polypropylene (iPP) using different types of phase modifiers. The influence of sulphonated EPDM, maleated EPDM, styrene‐ethylene‐co‐butylene‐styrene block copolymer, maleated PP, and acrylated PP as phase modifiers showed improved physico‐mechanical properties (like maximum stress, elongation at break, moduli, and tension set). Scanning electron and atomic force microscopy studies revealed better morphologies obtained with these phase modified EPDM‐iPP blends. The dependence of the phase modifier type and concentration was optimized with respect to the improvement in physical properties and morphology of the blends. Physical properties, dynamic mechanical properties, and morphology of these blends were explained with the help of interaction parameter, melt viscosity, and crystallinity of the blends. Theoretical modeling showed that Kerner, Ishai‐Cohen, and Paul models predicted the right morphology–property correlation for the prepared TPEs. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers.     

Structure and properties of dynamically cured EPDM/PP blends

The structure and properties of polyolefin blends of ethylene–propylene–diene terpolymer (EPDM) and polypropylene were studied. Blends were prepared in a laboratory internal mixer where EPDM was cured with PP under shear with dicumyl peroxide (DCP) at different shear conditions (blend–cure). Blends were also prepared for comparison from EPDM which were dynamically cured in the absence of PP and blended later (cure–blend). The effect of DCP concentration, intensity of the shear mixing, and rubber/plastic composition were studied. In blend–cure, the melt viscosity increased with increasing DCP concentration in blends of 75% EPDM and 25% PP, but it decreased with increasing DCP concentration in blends of 75% PP and 25% EPDM. In cure–blend, however, the melt viscosity increased with increasing DCP concentration for all compositions. The melt viscosity decreased with increasing intensity of the shear mixing presumably due to the formation of the smaller segregated microdomain of the crosslinked EPDM gels in both blend–cure and cure–blend materials. The crystallization rate was higher in EPDM/PP blends than in PP homopolymer. The crystallization rates for various blending conditions were also compared.     

氯化聚乙烯增容剂

叙述了氯化聚乙烯的结构、增容原理及氯含量为35%的氯化聚乙烯弹性体作为不相容聚合物共混物增容剂的应用。着重介绍了氯化聚乙烯在PVC/PE、PVC/PP、PVC/EPDM、PVC/SBS、SBR/HDPE/PVC、丁腈再生胶/SBR等不相容聚合物共混体系中的实际应用。     

氯化聚乙烯的研究与应用

综述了溶剂法、水相悬浮法和固相氯化法制备氯化聚乙烯(CPE)的特点。介绍了具有不同氯含量及结构的CPE性能及其在塑料、橡胶等领域的应用。重点阐述了在低密度聚乙烯／聚氯乙烯(PVC)、PVC／苯乙烯-丁二烯嵌段共聚物(SBS)、乙烯,乙烯-乙酸乙烯,炭黑共混体系和氯丁橡胶,甲基丙烯酸甲酯(MMA)、SBS／MMA接枝体系引入CPE对体系的增容、稳定、协同作用：以及CPE作为第三组分在高密度聚乙烯／PVC／CPE、苯乙烯-丙烯腈／CPE共混体系中对共混物形态、机械性能和流变性能的影响。     

Study on compatibilization-crosslinking synergism in PVC/LDPE blends

Influences of nitrile rubber (NBR, acrylonitrile content 33.5 – 36.5 wt.-%) on the structure and mechanical properties of poly(vinyl chloride) (PVC)/low density polyethylene (LDPE) blends and its synergism with crosslinking agent have been studied. The addition of NBR to the blend is accompanied by a decrease in domain size and improvements in mechanical properties of the blend. When dicumyl peroxide (DCP) is added to the blend together with NBR, good synergism is caused and mechanical properties will improve dramatically. It is concluded that NBR can promote the phase dispersion of PVC and LDPE and their interfacial adhesion. Then, the probability of DCP existing at the interface will increase and more co-crosslinked products will form. Therefore, compatibilization and crosslinking are both exerted sufficiently.     

Miscibility of blends of ethylene‐propylene‐diene terpolymer and polypropylene

The miscibility of polymers is not only an important basis for selecting a proper blending method, but it is also one of the key factors in determining the morphology and properties of the blends. The miscibility between ethylene‐propylene‐diene terpolymer (EPDM) and polypropylene (PP) was explored by means of dynamic mechanical thermal analysis, transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). The results showed that a decrease in the PP content and an increase of the crosslinking density of EPDM in the EPDM/PP blends caused the glass‐transition temperature peaks of EPDM to shift from a lower temperature to higher one, yet there was almost no variance in the glass‐transition temperature peaks of PP and the degree of crystallinity of PP decreased. It was observed that the blends prepared with different mixing equipment, such as a single‐screw extruder and an open mill, had different mechanical properties and blends prepared with the former had better mechanical properties than those prepared with the latter. The TEM micrographs revealed that the blends were composed of two phases: a bright, light PP phase and a dark EPDM phase. As the crosslinking degree of EPDM increased, the interface between the phases of EPDM and PP was less defined and the EPDM gradually dispersed in the PP phase became a continuous phase. The results indicated that EPDM and PP were both partially miscible. The mechanical properties of the blends had a lot to do with the blend morphology and the miscibility between the blend components. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 315–322, 2002     

Modification of Ethylene Propylene Diene Terpolymer Rubber by Some Thermoplastic Polymers

Abstract

Blends of ethylene propylene diene terpolymer (EPDM) rubber with thermoplastic polyolefins such as low‐density polyethylene (LDPE), high‐density polyethylene (HDPE), high molecular weight polypropylene (PP), and polypropylene random copolymer grade (PP‐R) were prepared by melt mixing. The physico‐mechanical properties, equilibrium swelling in benzene, and aging properties of the binary blends were investigated, analyzing the effect of the rubber/thermoplastics ratio and the type of the thermoplastic material on these properties. The data obtained indicate that EPDM/PP‐R blend in 20/80 w/w% shows the highest physico‐mechanical properties with improved retained tensile strength at 90°C for 7 days. This blend ratio also gives excellent retained equilibrium swelling in benzene at room temperature for 7 days, although EPDM/LDPE blend in 80/20 w/w% imparts the highest retained elongation at break at 90°C for 7 days.     

Influence of premade and in situ compatibilizers in polypropylene/ethylene–propylene–diene terpolymer thermoplastic elastomeric olefins and thermoplastic vulcanizates

During dynamic vulcanization of polypropylene (PP)/ethylene–propylene–diene terpolymer (EPDM) blends with dicumyl peroxide/triallyl cyanurate, there is a possibility of the generation of in situ graft links at the interface. Three potential compatibilizers (PP‐grafted EPDM, styrene–ethylenebutylene–styrene, and trans‐polyoctenamer) for PP/EPDM blends were first investigated as references to obtain a quantified insight into the effects to be expected from in situ graft links. Only the first compatibilizer showed some compatibilizing action in straight, unvulcanized blends, as evidenced by a slight increase in the tensile strength of the blend and a somewhat smaller EPDM particle size within the PP matrix. Also, dynamic mechanical testing, in particular, the glass‐transition temperatures of the PP and EPDM components, showed some signs of compatibilization. The PP‐grafted EPDM resembled most closely the structures of PP and EPDM. In the spectra obtained with high temperature, solid‐state NMR, there was an indication that PP–EPDM graft links were generated during the dynamic vulcanization process that still remained after the extraction of the free PP phase from the thermoplastic vulcanizate film. NMR relaxation experiments gave further evidence for the graft links formed in situ. In all cases, only qualitative indications could be achieved because of the extremely low number of graft links formed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3877–3888, 2006