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     

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     

Thermoplastic vulcanizates based on epoxidized natural rubber/polypropylene blends: Effect of epoxide levels in ENR molecules

Epoxidized natural rubbers (ENR) with various levels of epoxide groups were prepared. Thermoplastic vulcanizates based on 75/25 ENRs/PP blends with Ph‐PP compatibilizer were later prepared by dynamic vulcanization using sulfur curing system. Influence of various levels of epoxide groups on rheological, mechanical morphological properties, and swelling resistance of the TPVs was investigated. It was found that the mixing torque, apparent shear stress, apparent shear viscosity, tensile strength, and hardness properties increased with increasing levels of epoxide groups in the ENR molecules. This may be attributed to increasing level of chemical interaction between the methylol groups of the Ph‐PP molecules and polar functional groups of the ENR molecules. Also, the PP segments in the Ph‐PP molecules are capable of compatibilizing with the PP molecules used as a blend composition. In SEM micrographs, we observed finer dispersion of vulcanized rubber domains as increasing levels of epoxide contents. This corresponds to increasing trend of strength and hardness properties of the TPVs. An increasing trend of tension set and a decreasing trend of elongation at break were observed as increasing levels of epoxide groups in the ENR molecules. This is because of higher rigidity of the vulcanized ENR phase with higher epoxide groups. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3046–3052, 2006     

Effect of addition of polyoxypropylenediamine on the morphology and mechanical properties of maleated polypropylene/maleated rubber blends

Blends of maleated polypropylene and maleated ethylene propylenediene (EPDM-g-MA) were compounded in a twin-screw extruder with a polyetheramine (PEA), polyoxypropylenediamine, as a compatibilizer. The effect of the compatibilizer concentration and molecular weight on the physical properties was investigated. FTIR data showed that the addition of the compatibilizer caused an imide linkage to form between the amine functionality on the PEA and the maleic anhydride (MA) functionality on both the polypropylene (PP) and the rubber backbone. This bond improved the interfacial adhesion between the rubber and the PP matrix, resulting in an improvement in the toughness of the blends. Other improvements in the physical properties of the blends with a compatibilizer compared to the blends without it included notched Izod impact, elongation at yield, and elongation at break. The optimum improvement in properties was found when the level of the compatibilizer was about 3 wt %. These changes in properties correlated well with the morphology observed via optical and scanning electron microscopy. © 1998 John Wiley & Sons, Inc. J Appl Polm Sci 68: 1451–1472, 1998     

Thermoplastic vulcanizates based on poly(methyl methacrylate)/epoxidized natural rubber blends: Mechanical,thermal, and morphological properties

Epoxidized natural rubbers (ENRs) with epoxide levels of 10, 20, 30, 40 and 50 mol % were prepared. The ENRs were later used to prepare thermoplastic vulcanizates (TPVs) by blending them with poly(methyl methacrylate) (PMMA) using various formulations. Dynamic vulcanization, using sulfur as a vulcanizing agent, was performed during the mixing process. The mixing torque increased as the ENR contents and epoxide molar percentage increased. This was because of an increasing chemical interaction between the polar groups of the blend components, particularly at the interface between the elastomeric and thermoplastic phases. The ultimate tensile strength of the TPVs with ENR‐20 was high because of strain‐induced crystallization. ENRs with epoxide levels >30 mol % exhibited an increase of tensile strength because of increasing levels of chemical interaction between the molecules and the different phases. The hardness of the TPVs also increased with increased epoxide levels but decreased with increased contents of ENRs. Two morphology phases with small domains of vulcanized ENR particles dispersed in the PMMA matrix were observed from scanning electron microscopy micrographs. The TPVs based on ENR‐20 and ENR‐50 showed smaller dispersed rubber domains than those of the other types of ENRs. Furthermore, the size of the vulcanized rubber domain decreased with increasing amounts of PMMA in the blends. The decomposition temperature of the TPVs also increased as both the levels of ENRs in the blends and the epoxide molar percentage increased. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1251–1261, 2005     

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     

Dynamic mechanical properties and morphology of polypropylene/maleated polypropylene blends

The dynamic mechanical properties of both homopolypropylene (PPVC)/Maleated Poly-propylene (PP-g-MA) and ethylene-propylene block copolymer (PPSC)/Maleated Poly-propylene (PP-g-MA) blends have been studied by using a dynamic mechanical thermal analyzer (PL-DMTA MKII) over a wide temperature range, covering a frequency zone from 0.3 to 30 Hz. With increasing content of PP-g-MA, α relaxation of both blends gradually shift to a lower temperature and the apparent activation energy ΔE_α increases. In PPVC/PP-g-MA blends, β relaxation shifts to a higher temperature as the content of PP-g-MA increases from 0 to 20 wt % and then change unobviously for further varying content of PP-g-MA from 20 to 35 wt %. On the contrary, in the PPSC/PP-g-MA blends β₁ relaxation, the apparent activation energy ΔE_β1 and β₂ relaxation are almost unchanged with blend composition, while ΔE_β2 increases with an increase of PP-g-MA content. In the composition range studied, storage modulus É value for PPSC/PP-g-MA blends decreases progressively between β₂ and α relaxation with increasing temperature, but in the region the increment for PPVC/PP-g-MA blends is independent of temperature. The flexural properties of PPVC/PP-g-MA blend show more obvious improvement on PP than one of PPSC/PP-g-MA blends. Scanning electron micrographs of fracture surfaces of the blends clearly demonstrate two-phase morphology, viz. the discrete particles homogeneously disperse in the continous phase, the main difference in the morphology between both blends is that the interaction between the particles and the continuous phase is stronger for for PPVC/PP-g-MA than for PPSC/PP-g-MA blend. By the correlation of the morphology with dynamic and mechanical properties of the blends, the variation of the relaxation behavior and mechanical properties with the componenet structure, blend composition, vibration frequency, and as well as the features observed in these variation are reasonably interpreted. © 1996 John Wiley & Sons, Inc.     

Thermoplastic elastomers based on ionomeric polyblends of zinc salts of maleated polypropylene and maleated EPDM rubber

Ionomeric polyblends of the zinc salt of maleated EPDM rubber (Zn-mEPDM) and the zinc salt of maleated polypropylene (Zn-mPP) in the composition range from 90/10 to 60/40 wt% behave as ionic thermoplastic elastomers (ITPE), which show synergism in physical properties. The ionomeric polyblend shows higher physical properties than the corresponding non-ionomeric polyblend. Infrared spectroscopy reveals the occurrence of intermolecular ionic interactions between the component ionomers in the blend. Zinc stearate acts as a platicizer in the melt of the ionomeric polyblend, which exhibits a higher melt viscosity than the corresponding non-ionomeric polyblend. The blend can be reprocessed like a thermoplastic, with no drop in strength even after three extrusion cycles.     

共混比对预硫化多官能化丁基橡胶/天然橡胶共混胶性能的影响

研究了预硫化工艺下不同共混比对多官能化丁基橡胶/天然橡胶(MFIIR/NR)共混胶硫化特性、力学性能、耐老化性能以及微观形貌的影响,同时与传统工艺制备的共混胶的性能进行了对比。结果表明,当MFIIR作为主要组分时,预硫化法混炼胶的正硫化时间随MFIIR/NR共混比(质量比)的增大而缩短,最高转矩、最高转矩与最低转矩之差都随共混比的增大而呈现变小的趋势;随着预硫化法共混胶共混比的增大,共混胶的力学性能降低,耐老化性能提高,但都明显高于传统法共混胶的力学性能;预硫化共混胶拉伸断面的致密程度较传统法共混胶高,且随共混比的增大,拉伸断面的形貌趋于平坦。     

Effect of grafted maleic anhydride content and recyclability of dynamically cured maleated natural rubber/polypropylene blends

Maleated natural rubbers (MNRs) were prepared using various levels of maleic anhydride (MA) at 4, 6, 8, 10, and 12 phr. Dynamically cured 60/40 MNR/PP blends with phenolic‐modified polypropylene (Ph‐PP) compatibilizer at a loading level of 5 wt % of PP were prepared by melt mixing process using sulfur vulcanization system. The influence of the level of MA on properties of the thermoplastic vulcanizates (TPVs) was studied. It was found that the mixing torque, apparent shear stress, shear viscosity, tensile strength, and hardness properties increased with increasing levels of the MA or grafted succinic anhydride groups in the MNR molecules. This is attributed to an increase in chemical interaction and reaction between methylol groups in the Ph‐PP molecules and polar functional groups in the MNR molecules upon increasing levels of the grafted succinic anhydride groups. As a consequence, compatibilizing block copolymers of MNR and PP blocks were formed. The block copolymers were capable of compatibilizing with MNR and PP blend components via the respective blocks. Recyclability of the MNR/PP TPVs was also studied. It was found that, after processing through a number of cycles by injection molding and extrusion processing, the TPV exhibited marginal decreases in mechanical properties. This corresponded to slightly increasing size of the dispersed vulcanized rubber domains. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Cure characteristics and mechanical properties of hydrogenated natural rubber/natural rubber blends

The cure characteristics and mechanical properties of blends consisting of hydrogenated natural rubber (HNR) and natural rubber (NR) blends were investigated. The HNR/NR blends at 50/50 wt ratio were vulcanized using various cure systems: peroxide vulcanization, conventional vulcanization with peroxide, and efficient vulcanization with peroxide. The HNR/NR vulcanizates cured by the combination of peroxide and sulfur donor (tetramethylthiuram disulfide, TMTD) in the efficient vulcanization with peroxide exhibited the best mechanical properties. It was also found that the hydrogenation level of HNR did not affect the tensile strength of the vulcanizates. The tensile strength of the blends decreased with increasing HNR content because of the higher incompatibility to cause the noncoherency behavior between NR and HNR. However, the HNR/NR vulcanizate at 50/50 wt ratio showed the maximum ultimate elongation corresponding to a co‐continuous morphology as attested to by scanning electron micrographs. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermoplastic polyurethane/polypropylene blends based on novel vane extruder: A study of morphology and mechanical properties

Thermoplastic polyurethane (TPU) polypropylene (PP) blends of different weight ratios were prepared with a self‐made vane extruder (VE), which generates global dynamic elongational flow, and a traditional twin‐screw extruder (TSE), which generates shear flow. The mechanical properties, phase morphology, thermal behavior, and spherulite size of the blends were investigated to compare the different processing techniques. Samples prepared with a VE had superior mechanical properties than the samples prepared with a TSE. Scanning emission micrographs show that the fiber morphology of the TPU/PP blends (<60 wt% TPU) was improved by elongational flow in VE. Differential scanning calorimetry curves indicate that a dynamical elongational flow could improve the miscibility of the TPU/PP blends. The U‐shaped spherulite size curve indicates the changes in the spherulite size, as observed from a polarization microscope. Interlocked spherulites also reveal the apparent partial miscibility of the TPU/PP blends under elongational flow. POLYM. ENG. SCI., 54:716–724, 2014. © 2013 Society of Plastics Engineers     

The effect of peroxide crosslinking on thermal,mechanical, and rheological properties of polycaprolactone/epoxidized natural rubber blends

Polycaprolactone (PCL)/epoxidized natural rubber (ENR) blends (PCL/ENR = 70/30, 50/50 wt/wt) were prepared by a melt mixing in an internal mixer in the presence of a small amount (0.5 and 1 phr) of dicumyl peroxide. The effect of peroxide crosslinking on thermal, mechanical, and rheological properties of the blends was investigated by means of DSC, tensile test, and small amplitude oscillating rheometer, respectively. It was revealed that peroxide crosslinking enhanced degree of crystallinity of PCL phase and its non-isothermal melt crystallization temperature. The crosslinked blends behave like a thermoplastic elastomer exhibiting high elongation-at-break and fairly good elastic recovery as well as melt processibility. From melt rheological analysis, the peroxide crosslinked blends showed more pronounced shear thinning effect and higher elasticity compared to simple blends.     

马来酸酐和苯乙烯接枝改性对天然橡胶/聚丙烯共混物物理机械性能的影响

用动态硫化法制备了天然橡胶(NR)/聚丙烯(PP)热塑性弹性体(TPV)。研究了马来酸酐/苯乙烯/过氧化二异丙苯(MAH/St/DCP)多单体熔融接枝交联改性及纳米二氧化硅用量对NR/PP TPV物理机械性能的影响,讨论了NR/PP TPV的重复加工性能。结果表明,当MAH/St/DCP用量为3.750/1.875/0.375质量份、纳米二氧化硅用量为3质量份时,NR/PP TPV的物理机械性能最好,达到了国内外有关通用橡胶/PP TPV的水平,并且具有较好的重复加工性能。     

Morphology,mechanical and viscoelastic properties of nitrile rubber/epoxidized natural rubber blends

A new class of blend membranes from blends of nitrile rubber (NBR) and epoxidized natural rubber (ENR) has been prepared and their morphology, miscibility, mechanical, and viscoelastic properties have been studied. The ebonite method was used to study the blend morphology of the membranes. The morphology of the blends indicated a two‐phase structure in which the minor phase is dispersed as domains in the major continuous phase. The performance of NBR/ENR blend membranes has been studied from the mechanical measurements. The viscoelastic behavior of the blends has been analyzed from the dynamic mechanical data. An attempt was made to relate the viscoelastic behavior with the morphology of the blends. Various composite models have been used to predict the experimental viscoelastic data. The area under the linear loss modulus curve was larger than that obtained by theoretical group contribution analysis. The homogeneity of the system was further evaluated by Cole–Cole analysis. Finally, a master curve for the modulus of the blend was generated by applying the time–temperature superposition principle. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1561–1573, 2005     

Effect of maleimide curing on mechanical properties of ground tyre rubber/waste polypropylene blends

Abstract

Blends of ground tyre rubber and waste polypropylene with a maleimide curing system (50∶50 blends of ground tyre rubber/waste polypropylene) were prepared in a Haake Rheocord Polylab System, at 180°C and 90 rev min^–1 for 5 min. The curing agent and the activator used were N,N′-meta-phenylene dimaleimide (HVA-2) and di(tert-butylperoxyisopropyl) benzene (DTBPIB) respectively. The HVA-2 level varied from 0 to 5 parts per hundred parts (pphp), while the DTBPIB level varied from 0 to 1 pphp. Melt viscosity, tensile strength and elongation at break showed an increase with HVA-2 content, while the impact energy showed an optimum at 3 pphp level. The addition of the DTBPIB increased melt viscosity further and produced a homogeneous phase morphology of the blends. Impact energy improved with the DTBPIB level, while elongation at break and tensile strength showed an optimum at 0·6 pphp. Swelling behaviour and gel/sol from the boiled xylene extractions were studied, and the results obtained were correlated with the impact and tensile properties.     

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.     

Influences of blend proportions and curing systems on dynamic,mechanical, and morphological properties of dynamically cured epoxidized natural rubber/high‐density polyethylene blends

Thermoplastic elastomers (TPEs) based on dynamically cured epoxidized natural rubber/high‐density polyethylene (ENR/HDPE) blends were prepared. Influence of the process oil, blend proportion, and curing systems were investigated. It was found that the oil‐extended thermoplastic vulcanizates (TPVs) exhibited better elastomeric properties and improved ease of the injection process. Increasing the proportion of ENR caused increasing elastic response of elongation at break, tension set properties, and tan δ. It was also found that the TPV treated with phenolic resin exhibited superior mechanical properties and the smallest vulcanized rubber domains. The TPV treated with the conventional peroxide co‐agent curing system showed superior strength properties but had poor elastomeric properties. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

Enhancing the mechanical,morphological, and rheological behavior of polyethylene/polypropylene blends with maleic anhydride-grafted polyethylene

This is the first study to showcase the use of maleic anhydride-grafted polyethylene (MAPE) to compatibilize polyethylene (PE)-rich blends, where polypropylene (PP) represents the minor phase. By first mixing PP with MAPE, and then adding PE, MAPE was assumed to be localized at the PE/PP interface. Microscopy analysis confirmed that MAPE led to a remarkably fine PE/PP/MAPE morphology, with PP being uniformly dispersed into PE and having an average diameter 267% smaller than that in the PE/PP blend. According to mechanical and rheological tests, this translated into a 14%, 20%, and 14% enhancement of tensile strength, tensile modulus, and tensile toughness, respectively, as well as a 10% and 20% drop in PE/PP viscosity mismatch and interfacial tension, respectively. Finally, PE/PP/MAPE tensile toughness and elongation at break were greater than those of virgin PP, while PE/PP/MAPE strength and stiffness were similar to the ones of neat PP. Therefore, this study provides industries with the possibility to utilize products rich in PE instead of those made of more expensive PP, while still keeping the level of performance high; hence, creating a paradigm shift in the development of advanced lightweight polyolefin materials with tuned functionalities.     

Thermal and rheological properties of maleated polypropylene modified asphalt

Modified asphalts using polymeric additives, such as isotactic polypropylene (iPP) and maleated polypropylene (MPP), for asphalt binders were prepared and characterized for potential usages in pavement construction. The differential scanning calorimetry (DSC) studies show that most of the crystallinity of iPP remains intact in the asphalt binders, but MPP exhibits more interaction with the asphalt due to the increase of the amorphous region of MPP. The phase distributions and rheological properties of the modified asphalts were examined by scanning electron microscope (SEM) and dynamic shear rheometer (DSR), respectively. The images of SEM show that the MPP‐rich phase is larger than the iPP‐rich phase in asphalt blends, which contributes to more dispersion of the polymer into the asphalt phase in the asphalt/MPP blend. From the rheological studies, the asphalt blends containing iPP exhibit higher viscosity in terms of higher temperature to get Newtonian behavior and have a higher performance grade for rutting resistance at high temperature and frequency. POLYM. ENG. SCI., 45:1152–1158, 2005. © 2005 Society of Plastics Engineers