Thermoplastic vulcanizates based on epoxidized natural rubber/polypropylene blends: Effect of compatibilizers and reactive blending

Epoxidized natural rubber (ENR) was prepared using the performic epoxidation method. TPVs based on ENR/PP blends were later prepared by melt‐mixing processes via dynamic vulcanization. The effects of blend ratios of ENR/PP, types of compatibilizers, and reactive blending were investigated. Phenolic modified polypropylene (Ph‐PP) and graft copolymer of maleic anhydride on polypropylene molecules (PP‐g‐MA) were prepared and used as blend compatibilizers and reactive blending components of ENR/Ph‐PP and ENR/PP‐g‐MA blends. It was found that the mixing torque, apparent shear stress and apparent shear viscosity increased with increasing levels of ENR. This is attributed to the higher viscosity of the pure ENR than that of the pure PP. Furthermore, there was a higher compatibilizing effect because of the chemical interaction between the polar groups in ENR and PP‐g‐MA or Ph‐PP. Mixing torque, shear flow properties (i.e., shear stress and shear viscosity) and mechanical properties (i.e., tensile strength, elongation at break, and hardness) of the TPVs prepared by reactive blending of ENR/Ph‐PP and ENR/PP‐g‐MA were lower than that of the samples without a compatibilizer. However, the TPVs prepared using Ph‐PP and PP‐g‐MA as compatibilizers exhibited higher values. We observed that the TPVs prepared from ENR/PP with Ph‐PP as a compatibilizer gave the highest rheological and mechanical properties, while the reactive blending of ENR/PP exhibited the lowest values. Trend of the properties corresponds to the morphology of the TPVs. That is, the TPV with Ph‐PP as a blend compatibilizer showed the smallest rubber particles dispersed in the PP matrix, while the reactive blending of ENR/PP‐g‐MA showed the largest particles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4729–4740, 2006     

Improving low‐density polyethylene/poly(ethylene terephthalate) blends with graft copolymers

Blends of low‐density polyethylene (LDPE) and poly(ethylene terephthalate) (PET) were prepared with different weight compositions with a plasticorder at 240°C at a rotor speed of 64 rpm for 10 min. The physicomechanical properties of the prepared blends were investigated with special reference to the effects of the blend ratio. Graft copolymers, that is, LDPE‐grafted acrylic acid and LDPE‐grafted acrylonitrile, were prepared with γ‐irradiation. The copolymers were melt‐mixed in various contents (i.e., 3, 5, 7, and 9 phr) with a LDPE/PET blend with a weight ratio of 75/25 and used as compatibilizers. The effect of the compatibilizer contents on the physicomechanical properties and equilibrium swelling of the binary blend was investigated. With an increase in the compatibilizer content up to 7 phr, the blend showed an improvement in the physicomechanical properties and reduced equilibrium swelling in comparison with the uncompatibilized one. The addition of a compatibilizer beyond 7 phr did not improve the blend properties any further. The efficiency of the compatibilizers (7 phr) was also evaluated by studies of the phase morphology (scanning electron microscopy) and thermal properties (differential scanning calorimetry and thermogravimetric analysis). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

相容剂对NBR/PP共混型热塑性弹性体性能的影响

考察了普通氯化聚乙烯（ＣＰＥ）、高氯化ＣＰＥ、马来酸酐接枝聚丙烯及复合氯化聚丙烯（ＣＰＰ）等相容剂对ＮＢＲ／ＰＰ共混体系性能的影响。试验结果表明，复合ＣＰＰ是ＮＢＲ／ＰＰ共混体系的理想相容剂，其最佳用量为６份；以此为相容剂的ＮＢＲ／ＰＰ共混体系具有优良的热塑性，ＮＢＲ／ＰＰ共混型热塑性弹性体可采用热塑性塑料通用的加工方法进行加工。     

Influence of compatibilizers on the rheological,mechanical, and morphological properties of epoxidized natural rubber/polypropylene thermoplastic vulcanizates

In polymeric materials combining desirable properties, compatibility between constituent components of incompatible blends is necessary. The influence of two types of blend compatibilizers, a graft copolymer of maleic anhydride and polypropylene (PP) and phenolic‐modified PP, on the rheological, mechanical, and morphological properties of epoxidized natural rubber/PP thermoplastic vulcanizates was investigated at varied concentrations. All properties improved in a range of loading levels of compatibilizers at 0–7.5 wt % of PP. This was attributed to a chemical interaction between the different phases caused by the functionalized compatibilizers. Increasing chemical interaction between interfaces improved the interfacial tension and led to a microscale size of the dispersion. A decreasing trend in the properties was observed at compatibilizer levels higher than 7.5 wt % of PP because of segregation, which led to a third blend component dispersed in the PP matrix. The compatibilizers behaved as lubricants in the polymer melt flow. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

HPVC/SBR共混体系相容性的研究

采用动态硫化方法制备高聚合度聚氯乙烯（ＨＰＶＣ）／ＳＢＲ共混型热塑性弹性体,考察了单一组分相容剂「相容剂分别为ＮＢＲ２７０、ＮＢＲ Ｐ６５、ＣＰＥ和氢化苯乙烯－丁二烯、苯乙烯嵌段共聚物（ＳＥＢＳ）」、复合相容剂（ＳＥＢＳ／ＮＢＲ和ＣＰＥ／ＮＢＲ）及交联程度对ＨＰＶＣ／ＳＢＲ共混体系相容性的影响。结果表明,使用复合相容剂可明显改善ＨＰＶＣ／ＳＢＲ共混物的性能;动态硫化在改善共混物力学性能方面起主要作     

Poly(L‐lactide)/polypropylene blends: Evaluation of mechanical,thermal, and morphological characteristics

Poly(L lactide) (PLA) was blended with polypropylene (PP) at various ratios (PLA:PP = 90 : 10, 80 : 20, 70 : 30, and 50 : 50) with a melt‐blending technique in an attempt to improve the melt processability of PLA. Maleic anhydride (MAH)‐grafted PP and glycidyl methacrylate were used as the reactive compatibilizers to induce miscibility in the blend. The PLA/PP blend at a blend ratio of 90 : 10, exhibited optimum mechanical performance. Differential scanning calorimetry and thermogravimetric analysis studies showed that the PLA/PP/MAH‐g‐PP blend had the maximum thermal stability with the support of the heat deflection temperature values. Furthermore, dynamic mechanical analysis findings revealed an increase in the glass‐transition temperature and storage modulus with the addition of MAH‐g‐PP compatibilizer. The interaction between the compatibilizers and constituent polymers was confirmed from Fourier transform infrared spectra, and scanning electron microscopy of impact‐fractured samples showed that the soft PP phase was dispersed within the PLA matrix, and a decrease in the domain size of the dispersed phase was observed with the incorporation of MAH‐g‐PP, which acted as a compatibilizer to improve the compatibility between PLA and PP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

相容剂对CR/PVC热塑性弹性体的相容作用

研究了相容剂NBR和Elvaloy 741对CR／PVC共混物（共混比70／30）性能的影响,并通过透射电镜和红外光谱表征了相容剂NBR和Elvaloy 741对CR／PVC共混物的相容效果。结果表明,相容剂Elvaloy 741与CR和PVC之间的较强的相互作用,相容剂NBR和Elvaloy 741加入CR／PVC共混物中,使分散相尺寸变小;当相容剂用量为CR／PVC共混物中PVC用量的10％时,共昆物具有较好的综合性能。     

The Effect of Multiple Compatibilizers on the Impact Properties of Polypropylene/Polystyrene (PP/PS) Blend

Effects of compatibilizers on impact properties of polypropylene/ polystyrene (PP/PS) blends were studied and carried out through melt blending using co- rotating twin-screw extruder. A combination of two compatibilizers, maleic anhydride grafted polypropylene (PP-g-MA) and styrene maleic anhydride (SMA) was applied into PP/PS blends. Results from the Izod impact strengths, SEM observations and contact angle measurements in PP(50)/PS(50) blends indicated a better compatibilization effect with the use of dual compatibilizers. This was most probably due to improved adhesion between phases in PP/PS blend systems. The use of dual compatibilizers in the blend compositions produced higher impact properties in the PP/PS blend systems compared to single compatibilizer system.     

Influence of compatibilizer on mechanical,morphological and rheological properties of PP/ABS blends

The objective of this work was to study the compatibilizer effect on polypropylene (PP) and acrylonitrile butadiene styrene (ABS) blends. The blends were coextruded and injection molded in various ratios of ABS with and without compatibilizers. Universal testing machine was employed to analyze the tensile properties of basic PP/ABS binary blends. From the mechanical testing, the impact and tensile properties of PP/ABS blend were optimized at 80/20 weight ratio. Various compatibilizers such as PP-g-MAH, SEBS-g-MAH and ethylene α-olefin copolymer were used and their comparative performance on binary blend was enumerated. Hybrid compatibilization effect was also studied and reported. However, the addition of compatibilizers showed the maximum increase in impact strength attributed to rubber toughening effect of ABS. The effect of compatibilizers on morphological properties was examined using scanning electron microscopy (SEM). SEM micrographs depicted the more efficient dispersion of ABS particles in PP matrix with the addition of compatibilizers. Further, interparticle distance analysis was carried out to evaluate the rubber toughening effect. The ABS droplet size in compatibilized PP/ABS blend was brought to minimum of 3.2 μm from 9.9 μm with the addition of compatibilizers. The melt rheology of PP/ABS blend systems was investigated through parallel plate arrangement in frequency sweep. Linear viscoelastic properties like storage (G′) and loss (G″) modulus and complex viscosity (η*) have been reported with reference to the virgin materials. It is understood that the combination of compatibilizers (hybrid compatibilizer) had a considerable effect on the overall blend properties.     

The Effect of Epoxidized Natural Rubber (ENR-50) or Polyethylene Acrylic Acid (PEA) as Compatibilizer on Properties of Ethylene Vinyl Acetate (EVA)/Natural Rubber (SMR L) Blends

The effect of epoxidized natural rubber (ENR) or polyethylene acrylic acid (PEA) as a compatibilizer on properties of ethylene vinyl acetate (EVA)/natural rubber (SMR L) blends was studied. 5 wt.% of compatibilizer was employed in EVA/SMR L blend and the effect of compatibilizer on tensile properties, thermal properties, swelling resistance, and morphological properties were investigated. Blends were prepared by using a laboratory scale of internal mixer at 120°C with 50 rpm of rotor speed. Tensile properties, thermal properties, thermo-oxidative aging resistance, and oil swell resistance were determined according to related ASTM standards. The compatibility of EVA/SMR L blends with 5 wt.% of compatibilizer addition or without compatibilizing agent was compared. The EVA/SMR L blend with compatibilizer shows substantially improvement in tensile properties compared to the EVA/SMR L blend without compatibilizer. Compatibilization had reduced interfacial tension and domain size of ethylene vinyl acetate (EVA)/natural rubber (SMR L) blends.     

Thermoplastic elastomers based on epoxidized natural rubber and high‐density polyethylene blends: Effect of blend compatibilizers on the mechanical and morphological properties

Epoxidized natural rubber (ENR) with a level of epoxide groups of 20 mol % was prepared via the performic epoxidation method. It was then used to blend with high‐density polyethylene (HDPE) at various blend ratios. Three types of blend compatibilizers were prepared. These included a graft copolymer of HDPE and maleic anhydride (MA; i.e., HDPE‐g‐MA) and two types of phenolic modified HDPEs using phenolic resins SP‐1045 and HRJ‐10518 (i.e., PhSP‐PE and PhHRJ‐PE), respectively. We found that the blend with compatibilizer exhibited superior tensile strength, hardness, and set properties to that of the blend without compatibilizer. The ENR and HDPE interaction via the link of compatibilizer molecules was the polar functional groups of the compatibilizer with the oxirane groups in the ENR molecules. Also, another end of the compatibilizer molecules (i.e., HDPE segments) was compatibilizing with the HDPE molecules in the blend components. The blend with compatibilizer also showed smaller phase morphology than the blend without compatibilizer. Among the three types of the blend compatibilizer, HDPE‐g‐MA provided the blend with the greatest strength and hardness properties but the lowest set properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of curing agent and compatibilizer on the physicomechanical properties of polypropylene/nitrile butadiene rubber blends investigated by positron annihilation lifetime technique

A series of thermoplastic vulcanizates of polypropylene (PP)/nitrile butadiene rubber (NBR) (50/50) have been prepared by melt‐mixing method, using phenolic resin/SnCl₂ as the curing system and maleic anhydride‐functionalized PP (PP‐g‐MA) and carboxylated NBR (NBRE‐RCOOH) as the compatibilizing system. Triethylenetetramine was also employed to promote the reaction between the functionalized polymers. The effects of curing agent and compatibilizer on the mechanical and morphological properties have been studied. A novel technique based on positron annihilation lifetime spectroscopy has been used to measure the free volume parameters of these systems. The positron results showed minimum free volume size and free volume fraction at 5.0% of the curing agent suggesting some crosslinking in the rubber phase. The reduction in free volume holes at 2.5% of the compatibilizer is interpreted as improvement in the interfacial adhesion between the components of the blend. The observed variation of free volume fraction is opposite to the tensile strength and exhibits the correlation that, lesser the free volume more is the tensile strength at 2.5% of the compatibilizer in the blend. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4672–4681, 2006     

Rheological behavior of polyester blend and mechanical properties of the polypropylene–polyester blend fibers

The article deals with method of preparation, rheological properties, phase structure, and morphology of binary blend of poly(ethylene terephthalate) (PET)/poly(butylene terephthalate) (PBT) and ternary blends of polypropylene (PP)/(PET/PBT). The ternary blend of PET/PBT (PES) containing 30 wt % of PP is used as a final polymer additive (FPA) for blending with PP and subsequent spinning. In addition commercial montane (polyester) wax Licowax E (LiE) was used as a compatibilizer for spinning process enhancement. The PP/PES blend fibers containing 8 wt % of polyester as dispersed phase were prepared in a two‐step procedure: preparation of FPA using laboratory twin‐screw extruder and spinning of the PP/PES blend fibers after blending PP and FPA, using a laboratory spinning equipment. DSC analysis was used for investigation of the phase structure of the PES components and selected blends. Finally, the mechanical properties of the blend fibers were analyzed. It has been found that viscosity of the PET/PBT blends is strongly influenced by the presence of the major component. In addition, the major component suppresses crystallinity of the minor component phase up to a concentration of 30 wt %. PBT as major component in dispersed PES phase increases viscosity of the PET/PBT blend melts and increases the tensile strength of the PP/PES blend fibers. The impact of the compatibilizer on the uniformity of phase dispersion of PP/PES blend fibers was demonstrated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4222–4227, 2006     

Viscoelastic,thermo-mechanical and environmental properties of composites based on polypropylene/poly(lactic acid) blend and copper modified nanoclay

Poly(lactic acid) (PLA)/polypropylene (PP) blends composites were prepared by incorporating 3 wt.% of copper modified montmorillonite (MMT-Cu²⁺), obtained using cation exchange in a CuSO₄ solution, and 10 wt.% of polypropylene-graft-maleic anhydride (PP-g-MA) as a compatibilizer then varying the PLA content until 50 wt.%. These materials were subjected to several investigations such as X-rays diffraction, dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and tensile and environmental tests. The DMTA analysis showed that the glassy PLA high stiffness and the PP crystalline phase compensate the decrease in the storage modulus occurring during the PP and PLA glass transitions, respectively. The variations of tan δ revealed no changes on the PP and PLA phases glass transitions temperatures which indicate the immiscibility of the two polymers, as supported by DSC analysis. Blends composites SEM micrographs stated the immiscibility of the system resulting in the poor adhesion of the PLA droplets to the PP matrix. Also, the blends composites exhibited intermediate tensile properties between those of PP and PLA. The incorporation of MMT-Cu²⁺ to the (50/50) PP/PLA blend accentuated its aptitude to water absorption and ensured an efficient antimicrobial activity over a satisfactorily long period of around six months.     

Functionalization of polypropylene with oxazoline and reactive blending of PP with PBT in a corotating twin-screw extruder

The aim of this study was to prepare a compatibilized PP/PBT blend in a twin-screw extruder, using oxazoline-functionalized PP. First we prepared the functionalized PP (PP-g-OXA), and then we used it as a compatibilizer in the subsequent reactive blending stage. Polypropylene was successfully functionalized by ricinoloxazoline maleinate in a corotating twin-screw extruder using a melt free radical grafting technique. Grafting yields up to 2.1 phr were achieved. This functionalized PP used as a compatibilizer markedly improved the mechanical properties of the uncompatibilized PP/PBT (PBT content 30 wt %) blend. Significant improvements were observed, especially in impact strength (Charpy) and elongation at break of the compatibilized blends. The increased interactions between the phases were characterized by SEM analysis, DMTA, and DSC experiments. The properties of the blend greatly depended on the degradation of the PP during grafting. An optimal content of compatibilizer exists, which is dependent on the degradation of PP, grafting yield of oxazoline monomer, and on the amount of free, ungrafted monomer present in the compatibilizer. These factors can be adjusted by properly choosing the processing conditions and chemical parameters. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 883–894, 1997     

Compatibilization of Poly(propylene)/Polyamide 6 Blends with Functionalized Poly(propylene)s Prepared with Metallocene Catalyst

Summary: Propylene was copolymerized with 10‐undecen‐1‐ol using dimethylsilanylbis(2‐methyl‐4‐phenyl‐1‐indenyl)zirconium dichloride as catalyst and MAO and TIBA as cocatalysts. Comonomer incorporations from 0.1 to 0.9 mol‐% (0.5 to 3.6 wt.‐%) were obtained. These hydroxyl functionalized copolymers were applied as compatibilizers to PP/PA6 blend with a composition of 70/30. For comparison, hydroxyl functionalized polyethylene prepared with metallocene catalyst and commercial MAH grafted ethylene butyl acrylate (E/BA/MAH) and poly(propylene) (PP‐g‐MAH) were also used as compatibilizers. Effects of the compatibilizers on morphology and mechanical and thermal properties of the blends were studied. Enhanced adhesion between the blend components was observed in morphology and dynamic mechanical studies. Although improvement in toughness was not as pronounced as expected, there were indications that the hydroxyl functionalized propylene copolymers prepared with metallocene catalysts could serve as a new type of compatibilizer in polymer blends.

SEM micrograph (5 000×) of an PP/PA6/PP‐co‐OH4 blend.     

Effect of a hybrid compatibilizer on the mechanical properties and interfacial tension of a ternary blend with polypropylene,poly(lactic acid), and a toughening modifier

This study examined the effect of three compatibilizers, namely, a hybrid compatibilizer composed of polypropylene‐maleic anhydride (PP‐g‐MAH) and polyethylene‐glycidyl methacrylate (PE‐g‐GMA), a single compatibilizer composed of PP‐g‐MAH, and a single compatibilizer composed of PE‐g‐GMA, on the mechanical, morphological, and rheological properties of a ternary blend of polypropylene (PP), poly(lactic acid; PLA), and a toughening modifier. The results of tensile strength, flexural strength, and impact strength tests for the ternary blends before and after hydrolysis, revealed that the ternary blend with a hybrid compatibilizer content of 3 phr exhibited better material properties than the blend containing a single compatibilizer. In the weighted relaxation spectra of the ternary blend using the Palierne emulsion model, the ternary blend containing the hybrid compatibilizer, exhibited only one relaxation spectrum peak at ∼ 0.16 s. This result suggests that the ternary blend with the hybrid compatibilizer exhibits uncharacteristic morphological properties, that is, a single‐phase microstructure. The above results suggest that the hybrid mixture is an effective compatibilizer for the ternary blend of PP, PLA, and a toughening modifier. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Preparation and characterization of acrylonitrile–styrene–methylmethacrylate terpolymer as a compatibilizer for rubber blends

Acrylonitrile‐co‐styrene‐co‐methylmethacrylate (AN‐S‐MMA) terpolymer was prepared by bulk and emulsifier‐free emulsion polymerization techniques. The bulk and emulsion terpolymers were characterized by means of Fourierr transform infrared spectroscopy, ¹³C nuclear magnetic resonance (NMR) spectroscopy, gel permeation chromatography, thermal gravimetric analysis, and elemental analysis. The kinetics of the terpolymerization were studied. The terpolymers were then incorporated into butadiene—acrylonitrile rubber (NBR)/ethylene propylene diene monomer rubber (EPDM) blends and into chloroprene rubber (CR)/EPDM blend. The terpolymers were then tested for potential as compatibilizers by using scanning electron microscopy and differential scanning calorimetry. The terpolymers improved the compatibility of CR/EPDM and NBR/EPDM blends. The physicomechanical properties of CR/EPDM and NBR/EPDM blend vulcanizates revealed that the incorporation of terpolymers was advantageous, since they resulted in blend vulcanizates with higher 100% moduli and with more thermally stable mechanical properties than the individual rubbers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3143–3153, 2003     

Study of the modification of the properties of (PP/EPR) blends with a view to preserving natural resources when elaborating new formulation and recycling polymers

The aim of the present work is to study how CaCO₃, very abundant on earth, can be blended with polypropylene/ethylene propylene rubber (PP/EPR) either to preserve natural resources when elaborating virgin formulations or to simulate mixtures of waste made of CaCO₃ filled PP with PP/EPR which could result from end-of-life-vehicles (ELV). The article focuses on the studies of PP/EPR blends, used in the manufacture of automobile fenders, in the presence of nano-CaCO₃ and compatibilizers. Blends of various compositions (with and without compatibilizer and nanoparticles) were prepared using a corotating twin-screw extruder. The results were compared with the ones presented by a commercial (PP/EPR) blend. The experiments included mechanical tests, differential scanning calorimetry, scanning electron microscopy, and dynamic mechanical analysis experiments. The presence of the compatibilizers in the (PP/EPR) blends decreases the size of elastomer particles, improves the adherence to the interface and improves the mechanical properties. The nano-CaCO₃ would also seem to act as a nucleating agent in the PP/EPR matrix; it increases the cristallinity and the Young modulus of the blends. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Evolution of the morphological and rheological properties along the extruder length for compatibilized blends of a commercial liquid‐crystalline polymer and polypropylene

In a previous article, we reported on the evolution of the morphological and rheological properties along the length extruder for blends of a liquid‐crystalline polymer (LCP), Rodrun LC3000, and polypropylene (PP). In this work, we extended this study to compatibilized PP/Rodrun LC3000 blends, containing 10 wt % LCP and different compatibilizers, to determine the influence of the addition of a compatibilizer during the processing and, consequently, on the final properties of such systems. The results revealed that the addition of compatibilizers led to a decrease in the mean diameters of the LCP structures, in comparison with those presented by the noncompatibilized blend containing the same LCP content. This phenomenon occurred more quickly for those blends in which compatibilization was carried out in an efficient way. Linear oscillatory shear was mainly sensitive to the type of morphology present in the blends, whereas nonlinear oscillatory shear was more sensitive to the evolution in the droplet/fibril size and along the extruder length. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 347–359, 2006